Polyarylene Sulfide Film

ABSTRACT

It is aimed to provide a polyarylene sulfide film for an acoustic instrument vibrating plate excellent in heat resistance, molding processability, acoustic properties, and also heat moldability. Provided is a polyarylene sulfide film wherein the elongation at break in either a longitudinal direction or a width direction of the film is 100% or more and 250% or less, and the Young&#39;s modulus in either a longitudinal direction or a width direction of the film is 1.5 GPa or more and less than 4 GPa.

TECHNICAL FIELD

The present invention relates to a polyarylene sulfide film for anacoustic instrument vibrating plate constituting various kinds ofacoustic instruments i.e., speakers, and relates to a polyarylenesulfide film excellent in heat moldability.

BACKGROUND ART

Conventionally, as an acoustic instrument vibrating plate made ofplastic, there have been used acoustic instrument vibrating plates madeof polyethylene terephthalate (PET) film, and also polyethylenenaphthalate (PEN) or polyetherimide (PEI) having better heat resistanceand rigidity than PET (see Patent documents 1, 2, and 3).

However, in the case where an acoustic instrument vibrating plate usingPET is employed in a speaker of a small diameter, for example, for acellular phone, thermal deformation easily occurs in an atmosphere at65° C. or more, and heat resistance is not sufficient. On the otherhand, an acoustic vibrating plate of PEN is better in heat resistancethan a vibrating plate made of PET but still not sufficient in heatresistance. Further, regarding an acoustic vibrating plate of PEI, therehave been problems that acoustic properties are deteriorated dependingon a shape of speaker vibrating plate, and breakage of film occurs dueto not withstanding a larger external power output. Therefore, anacoustic vibrating plate made of polyphenylene sulfide (PPS) excellentin heat resistance and mechanical properties has been proposed (Patentdocument 4), but moldability is not sufficient, there has been a problemthat a film is broken in heat molding. Further, a film made of PPS andpolyetherimide has been proposed (Patent document 5), but moldability isnot sufficient and there has been a problem that a film is broken inheat molding.

Patent document 1: Japanese Unexamined Patent Publication No. 1-67099Patent document 2: Japanese Unexamined Patent Publication No. 62-263797Patent document 3: Japanese Examined Patent Publication No. 4-68839Patent document 4: Japanese Unexamined Patent Publication No. 6-305019Patent document 5: Japanese Unexamined Patent Publication No.2001-261959

DISCLOSURE OF THE INVENTION Problem to be Solved by the Invention

The present invention is based on the finding of a film for a speakervibrating plate capable of solving these problems, specifically, toprovide a polyarylene sulfide film having excellent heat resistance,molding processability and acoustic properties, and further apolyarylene sulfide film excellent in heat moldability.

Means to Solve the Problem

The present invention has the following constitutions to solve theabove-described problem.

Namely,

(1) A polyarylene sulfide film wherein the elongation at break in eithera longitudinal direction or a width direction of the film is 100% ormore and 250% or less, and the Young's modulus in either a longitudinaldirection or a width direction of the film is 1.5 GPa or more and lessthan 4 GPa.(2) The polyarylene sulfide described in (1), wherein the elongation atbreak in both a longitudinal direction and a width direction of the filmis 100% or more and 250% or less, and the Young's modulus in both alongitudinal direction and a width direction of the film is 1.5 GPa ormore and less than 4 GPa.(3) The polyarylene sulfide film described in (1), wherein the thicknessof the film is 3 μm or more and 100 μm or less.(4) The polyarylene sulfide film described in (1), comprising athermoplastic resin (Y) other than polyarylene sulfide, wherein thecontent of the thermoplastic resin (Y) is 1 to 40 parts by weight whenthe sum of contents of the polyarylene sulfide and the thermoplasticresin (Y) is 100 parts by weight.(5) The polyarylene sulfide film described in (1), comprising an inertparticle by 0.1 to 30 parts by weight relative to 100 parts by weight intotal of polymers constituting the film.(6) The polyarylene sulfide film described in (4), comprising an inertparticle by 0.6 to 30 parts by weight relative to 100 parts by weight intotal of polymers constituting the film, and a thermoplastic resin (Y)other than polyarylene sulfide by 1 to 40 parts by weight relative to100 parts by weight in total of polymers constituting the film.(7) The polyarylene sulfide film described in (5), wherein the particlediameter of the inert particle is 0.1 μm or more and 3 μm or less.(8) The polyarylene sulfide film described in (5), wherein the inertparticle is at least one kind selected from the group consisting ofcalcium carbonate and silica.(9) The polyarylene sulfide film described in (4), wherein thethermoplastic resin (Y) is at least one kind selected from the groupconsisting of polyamide, polyetherimide, polysulfone and polyethersulfone.(10) The polyarylene sulfide film described in (4), wherein the averagedispersion diameter of the thermoplastic resin (Y) is 0.01 to 2 μm.(11) The polyarylene sulfide film described in (4), wherein the averagedispersion diameter of the thermoplastic resin (Y) is 0.05 to 0.5 μm.(12) The polyarylene sulfide film described in (1), wherein thepolyarylene sulfide is polyphenylene sulfide.(13) The polyarylene sulfide film described in (1), which is a film forheat molding.(14) The polyarylene sulfide film described in (1), which is a film foran acoustic instrument vibrating plate.(15) The polyarylene sulfide film described in (1), wherein the glasstransition temperature thereof is observed at 85° C. or more to lessthan 95° C., and not observed at 95° C. or more to 130° C. or less.(16) The polyarylene sulfide film described in (4), comprising a siliconatom constituting a siloxane bond in an interface of a dispersed phasecomposed of the thermoplastic resin A.(17) A method of producing the polyarylene sulfide film described in(1), comprising the step of subjecting a resin composition obtained bykneading raw materials comprising polyarylene sulfide, thermoplasticresin A, and 0.1 to 10 parts by weight of a compatible plasticizerhaving at least one kind of group selected from the group consisting ofan epoxy group, an amino group and an isocyanate group to a meltfilm-forming.

EFFECT OF THE INVENTION

According to the present invention, as explained below, it is possibleto obtain a polyarylene sulfide film excellent in heat resistance,molding processability and acoustic properties, further a polyarylenesulfide film excellent in heat moldability.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross sectional view showing an Example of an acousticinstrument vibrating plate using the present invention.

FIG. 2 is a cross sectional view of a speaker using an acousticinstrument vibrating plate of the present invention.

DESCRIPTION OF NUMBER AND SYMBOL

-   1. Acoustic instrument vibrating plate-   1 a. Dome part of acoustic instrument vibrating plate-   1 b. Concave part of acoustic instrument vibrating plate-   1 c. Peripheral part of acoustic instrument vibrating plate-   1 d. External attaching part of acoustic instrument vibrating plate-   2. Speaker equipped with acoustic instrument vibrating plate-   3. Voice coil-   4. Upside magnetic pole plate of speaker-   5. Downside magnetic pole plate of speaker-   6. Magnetic space-   7. External element of speaker-   8. Gasket-   9. Magnet of speaker-   10. Magnetic circuit of speaker-   11. Frame-   12. Protector

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, polyarylene sulfide films of the present invention will beexplained. The polyarylene sulfide film of the present invention isexcellent in heat resistance, moldability, acoustic properties, andparticularly heat moldability. To exhibit these characteristics, in thepresent invention, it is necessary that the elongation at break ineither a longitudinal direction or a width direction of the film is 100%or more and 250% or less. A more preferable range of the elongation atbreak is 110% or more and 230% or less, a further preferable range is120% or more and 210% or less. When the elongation at break is less than100%, a film is sometimes torn or broken in processing into a speakervibrating plate. On the other hand, when the elongation at break exceeds250%, it is necessary to make a draw ratio in film-forming extremelylow, there arise problems that unevenness of quality generates in awidth direction of a film and acoustic properties are lowered. To set anelongation at break of a film in the range of the present invention, adraw ratio in a longitudinal direction or width direction in producing afilm is 2.2 to 5, preferably 2.4 to 4.5, further preferably 2.6 to 4,and most preferably 3.0 to 3.5. Further, heat-set of this stretched filmunder extension or relaxing in a width direction tends to obtain theeffect of the present invention. Further, other than film-formingconditions, the effect of the present invention is more easily obtainedin such manner that a thermoplastic resin (Y) other than polyarylenesulfide is contained in a preferable range of the present invention.

Further, the polyarylene sulfide film of the present invention has theYoung's modulus in either a longitudinal direction or a width directionof the film of 1.5 GPa or more and less than 4 GPa. A more preferablerange of Young's modulus is 1.7 GPa or more and less than 3.8 GPa, andfurther preferable range is 1.9 GPa or more and less than 3.6 GPa. Afilm with Young's modulus of less than 1.5 Gpa tends to become uneven infilm thickness, and since the film easily deforms in handling, handlingthe film becomes difficult. On the other hand, when the Young's modulusexceeds 4 Gpa, a film is sometimes torn or broken in processing into aspeaker vibrating plate, there is a case that acoustic properties aredeteriorated. To set the Young's modulus of a film in the range of thepresent invention, a draw ratio in a longitudinal direction and widthdirection in producing a film is 2.2 to 5, preferably 2.4 to 4.5,further preferably 2.6 to 4, and most preferably 3.0 to 3.5. Further,heat-set of this stretched film under extension or relaxing in a widthdirection tends to obtain the effect of the present invention.

Further, the polyarylene sulfide film of the present invention is apreferable aspect from the viewpoint of further improving moldabilitywhen the elongation at break in both a longitudinal direction and awidth direction of the film is 100% or more and 250% or less. A morepreferable range of the elongation at break is 110% or more and 230% orless, a further preferable range is 120% or more and 210% or less. Whenthe elongation at break is less than 100%, a film is sometimes torn orbroken in processing into a speaker vibrating plate. On the other hand,when the elongation at break exceeds 250%, it is necessary to make adraw ratio in film-forming extremely low, there arise problems thatunevenness of quality generates in a width direction of a film andacoustic properties are lowered. To set an elongation at break of a filmin the range of the present invention, a draw ratio in a longitudinaldirection and width direction in producing a film is 2.2 to 5,preferably 2.4 to 4.5, further preferably 2.6 to 4, and most preferably3.0 to 3.5. Further, heat-set of this stretched film under extension orrelaxing in a width direction tends to obtain the effect of the presentinvention. Further, other than film-forming conditions, the effect ofthe present invention is more easily obtained in such manner that athermoplastic resin (Y) other than polyarylene sulfide is contained in apreferable range of the present invention.

Further, the polyarylene sulfide film of the present invention has theYoung's modulus in both a longitudinal direction and a width directionof the film of 1.5 GPa or more and less than 4 GPa from the viewpoint offurther improving moldability. A more preferable range of Young'smodulus is 1.7 GPa or more and less than 3.8 GPa, and further preferablerange is 1.9 GPa or more and less than 3.6 GPa. A film with Young'smodulus of less than 1.5 Gpa tends to become uneven in film thickness,and since the film easily deforms in handling, handling the film becomesdifficult. On the other hand, when the Young's modulus exceeds 4 Gpa,there is a case that acoustic properties are deteriorated.

As the polyarylene sulfide of the present invention, there can be used ahomopolymer or copolymer having a repeating unit of —(Ar—S)—. As the Ar,a unit expressed by the following formulas (A) to (K) can be mentioned.

wherein R1 and R2 are substituents selected from hydrogen, an alkylgroup, an alkoxy group and a halogen group, R1 and R2 may be the same ordifferent.

As the repeating unit of polyarylene sulfide used in the presentinvention, a structural formula expressed by the above-described formula(A) is preferable, and typical examples thereof include polyphenylenesulfide, polyphenylene sulfide sulfone, polyphenylene sulfide ketone,random copolymer and block copolymer thereof, and a mixture thereof. Inparticular, as a preferable polyarylene sulfide, polyphenylene sulfide(PPS) is preferably exemplified from the viewpoints of property of filmand economic efficiency of film, it is a resin containing preferably 80mol % or more of p-phenylene sulfide unit as a major constitutional unitof a polymer shown in the following structural formula, more preferably90 mol % or more. When such p-phenylene sulfide component is less than80%, crystallizability, glass transition temperature and the like arelow, and heat resistance, dimensional stability, mechanicalcharacteristic, dielectric characteristic and the like characterized byPPS are sometimes damaged.

In the above-described PPS resin, when it may contain a unit of othercopolymerizable sulfide bond as long as which is less than 20 mol % ofrepeating units, preferably less than 10 mol %. As the repeating unit ofless than 20 mol % of repeating units, preferably less than 10 mol %,for example, there are exemplified a three-functional group, an etherunit, a sulfone unit, a ketone unit, a meta-bond unit, an aryl grouphaving a substituent group such as an alkyl group, a biphenyl unit, ater-phenylene unit, a vinylene unit and a carbonate unit, as a specificexample, the following structural units can be mentioned. It is possibleto be constituted by at least one or two among them. In this case, theconstitutional unit may be from any copolymerization method of a randomtype or block type.

The melt viscosity of PPS resin is not particularly limited as long asit can provide melt-kneading, it is preferably in a range of 100 to2,000 Pa·s under a shear rate of 1,000 (1/sec) at a temperature of 315°C., and more preferably in a range of 200 to 1,000 Pas.

PPS resin for the present invention can be produced by various methods,for example, a method for obtaining a polymer having a relatively smallmolecular weight described in Japanese Examined Patent Publication No.45-3368, or a method for obtaining a polymer having a relatively largemolecular weight described in Japanese Examined Patent Publication No.52-12240 and Japanese Unexamined Patent Publication No. 61-7332.

In the present invention, the PPS resin obtained can be used after beingconducted by various treatments such as crosslinking/molecular weightheightening by heating in air; heat treatment under inert gas atmospheresuch as nitrogen or reduced pressure; wash with an organic solvent, hotwater and aqueous acid solution; and activation by a compound having afunctional group such as acid anhydride, amine, isocyanate andfunctional disulfide compound.

Next, the production method of PPS resin is exemplified, but the presentinvention is not limited thereto.

For example, sodium sulfide and p-dichlorobenzene are reacted in anamide based polar solvent such as N-methyl-2-pyrrolidone (NMP) underhigh temperature and high pressure. If necessary, a copolymerizablecomponent such as trihalobenzene can be contained. As a polymerizationdegree adjusting agent, caustic potash or alkali metal carboxylate isadded and a mixture is subjected to polymerization reaction at 230 to280° C. After polymerization, a polymer is cooled, the polymer is madeinto an aqueous slurry and filtered to obtain a granular polymer. Thispolymer is stirred in aqueous solution of acetate or the like at 30 to100° C. for 10 to 60 minutes, washed with ion-exchanged water at 30 to80° C. several times, and dried to obtain PPS powders. The powderypolymer is washed with NMP at an oxygen partial pressure of 10 torrs orless, preferably 5 torrs or less, then washed with ion-exchanged waterat 30 to 80° C. several times, and dried under a reduced pressure of 5torrs or less. The thus obtained polymer is a substantially liner PPSpolymer, thus it can be subjected to a stable stretching film-forming.Apparently, if necessary, there may be added other polymeric compounds,inorganic and organic compounds such as silicon oxide, magnesium oxide,calcium carbonate, titanium oxide, aluminum oxide, crosslinkedpolyester, crosslinked polystyrene, mica, talc and kaolin, heatdecomposition preventing agent, heat stabilizer and antioxidant.

As a specific method in the case of the crosslinking/molecular weightheightening by heating a PPS resin, it can be exemplified a method ofcarrying out heating under an oxidative atmosphere such as air andoxygen, or under a mixed gas atmosphere of the oxidative atmosphere andan inert gas such as nitrogen and argon in a heating container at apredetermined temperature until obtaining a desired melt viscosity. Theheat treatment temperature is ordinarily selected at 170 to 280° C.,more preferably 200 to 270° C., and the heat treatment time isordinarily selected for 0.5 to 100 hours, more preferably for 2 to 50hours, by controlling these two, a resin having a target melt viscositycan be obtained. As apparatus for the heat treatment, it may be anordinary hot-air dryer, or a heating apparatus in rotary type or withagitating blades, to perform an efficient and uniform treatment, it ispreferable to use a heating apparatus in rotary type or with agitatingblades.

As a specific method for heat treatment of PPS resin under an inert gasatmosphere such as nitrogen or reduced pressure, there can beexemplified a method for heat treatment that, under an inert gasatmosphere such as nitrogen or reduced pressure, the heat treatmenttemperature is 150 to 280° C., more preferably 200 to 270° C., and theheat treatment time is 0.5 to 100 hours, more preferably for 2 to 50hours. As apparatus for the heat treatment, it may be an ordinaryhot-air dryer, or a heating apparatus in rotary type or with agitatingblades, to perform an efficient and more uniform treatment, it ispreferable to use a heating apparatus in rotary type or with agitatingblades. The PPS resin used in the present invention is preferably asubstantially linear PPS without heightening a molecular weight bythermal oxidation-crosslinking treatment to achieve the aim at improvingan elongation at break.

The PPS resin used in the present invention is preferably a PPS resinthat deionization treatment is conducted. As a specific example of thedeionization treatment, there can be exemplified an aqueous acidsolution wash treatment, a hot water wash treatment, an organic solventwash treatment and the like, and these treatments may be used incombination with 2 or more kinds of methods.

As a specific method for an organic solvent wash treatment of PPS resin,the following methods can be exemplified. Namely, as an organic solvent,it is not particularly limited as long as it has no function ofdecomposing a PPS resin, for example, there are listednitrogen-containing polar solvents such as N-methylpyrrolidone,dimethylformamide and dimethylacetoamide; sulfoxide/sulfone basedsolvents such as dimethyl sulfoxide and dimethyl sulfone; ketone basedsolvents such as acetone, methyl ethyl ketone, diethyl ketone andacetophenone; ether based solvents such as dimethyl ether, dipropylether and tetrahydrofuran; halogen based solvents such as chloroform,methylene chloride, trichloroethylene, ethylene dichloride,dichloroethane, tetrachloroethane and chlorobenzene; alcohol/phenolbased solvents such as methanol, ethanol, propanol, butanol, pentanol,ethylene glycol, propylene glycol, phenol, cresol and polyethyleneglycol; aromatic hydrocarbon based solvents such as benzene, toluene andxylene. Among these organic solvents, N-methylpyrrolidone, acetone,dimethylformamide and chloroform are particularly preferably used.Further, these organic solvents may be used alone or in a mixture of 2or more kinds.

As a method for washing with an organic solvent, there is a method thata PPS resin is immersed in an organic solvent, if necessary, suitablestirring or heating is also possible. The washing temperature in washinga PPS resin with an organic solvent is not particularly limited, and anarbitrary temperature can be selected in a range of ambient temperatureto 300° C. As the washing temperature increases, washing efficiencytends to be higher, and a sufficient effect can be ordinarily obtainedin a temperature from ambient temperature to 150° C. Further, it ispreferable to wash a PPS resin conducted by an organic solvent wash byusing water or warm water several times to remove the remaining organicsolvent therein.

As a specific method for hot-water wash treatment of PPS resin, thefollowing methods can be exemplified. Namely, to exhibit an effect ofpreferable chemical modifications of PPS resin by hot-water wash, waterused is preferably distilled water or ion-exchanged water. The operationof hot water treatment is carried out ordinarily by pouring apredetermined amount of PPS resin into a predetermined amount of water,and heating and stirring at ambient pressure or in a pressure container.The ratio of PPS resin to water is preferably water-rich, ordinarilybath ratio is selected such that PPS is 200 g or less relative to oneliter of water.

As a specific method for aqueous acid solution wash treatment of PPSresin, the following methods can be exemplified. Namely, there is amethod that a PPS resin is immersed in an acid or aqueous acid solution,if necessary, suitable stirring or heating is also possible. The acidused is not particularly limited as long as it has no function ofdecomposing a PPS resin, there are listed aliphatic saturatedmonocarboxylic acids such as formic acid, acetic acid, propionic acidand butyric acid; halogen-substituted aliphatic saturated monocarboxylicacids such as chloroacetic acid and dichloroacetic acid; aliphaticunsaturated monocarboxylic acids such as acrylic acid and crotonic acid;aromatic carboxylic acids such as benzoic acid and salicylic acid;dicarboxylic acids such as oxalic acid, malonic acid, succinic acid,phthalic acid and fumaric acid; and inorganic acidic compounds such assulfuric acid, phosphoric acid, hydrochloric acid, carbonic acid andsilicic acid. Among them, acetic acid and hydrochloric acid arepreferably used. It is preferable to wash a PPS resin conducted by acidtreatment by using water or warm water several times to remove theremaining acid or salt therein. Further, water used for washing ispreferably distilled water or ion-exchanged water from the viewpoint notdamaging an effect of preferable chemical modifications of PPS resin byacid treatment. When aqueous acid solution wash treatment is conducted,acid terminal components of PPS resin increase, in mixing with otherthermoplastic resin, which is preferable because an enhancing effect ofdispersion mixing performance is easily obtained.

In the polyarylene sulfide film of the present invention, it ispreferable to comprise a thermoplastic resin (Y) because moldingprocessability and acoustic properties in the present invention areimproved, in particular, heat moldability is improved. As thethermoplastic resin (Y), for example, there can be used various kinds ofpolymers such as polyamide, polyetherimide, polyether sulfone,polysulfone, polyphenylene ether, polyester, polyarylate,polyamideimide, polycarbonate, polyolefin, and polyetheretherketone; anda blend containing at least one kind of these polymers. In the presentinvention, the thermoplastic resin (Y) is preferably polyamide,polyetherimide, polyether sulfone and polysulfone from the viewpoints ofaffinity for polyarylene sulfide and exhibition of the effect of thepresent invention.

Polyamide preferably used as the thermoplastic resin (Y) is notparticularly limited as long as it is a known polyamide, it is generallya polyamide composed of amino acid, lactam or diamine and dicarboxylicacid as major constitutional components. As a typical example of themajor constitutional component, there are listed amino acids such as6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acidand para-amiomethylbenzoic acid; lactams such as ∈-aminocaprolactam andω-laurolactam; aliphatic, alicyclicand aromatic diamines such astetramethylenediamine, hexamethylenediamine, undecamethylenediamine,dodecamethylenediamine, 2,2,4-/2,4,4-trimethylhexamethylenediamine,5-methylnonamethylenediamine, meta-xylenediamine, para-xylenediamine,1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane,1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane,bis(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane,2,2-bis(4-aminocyclohexyl)propane, bis(aminopropyl)piperazine,aminoethylpiperazine and 2-methylpentamethylenediamine; and aliphatic,alicyclic and aromatic dicarboxylic acids such as adipic acid, spericacid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid,isophthalic acid, 2-chloroterephtahlic acid, 2-methylterephthalic acid,5-methylisophthalic acid, 5-sodiumsulfoisophthalic acid,hexahydroterephthalic acid and hexahydroisophthalic acid, in the presentinvention, there can be used a polyamide homopolymer or copolymerderived from these raw materials each alone or in a mixture thereof.

In the present invention, as a useful polyamide, there are listedhomopolyamide resins such as polycaproamide (nylon 6), polyhexamethyleneadipamide (nylon 66), polytetramethylene adipamide (nylon 46),polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide(nylon 612), polydodecanamide (nylon 12), polyundecanamide (nylon 11),polyhexamethylene terephthalamide (nylon 6T) and polyxylene adipamide(nylon XD6), or copolymers of thereof, such as copolyamide resins (nylon6/66, nylon 6/66/610, 66/6T) and the like. These polyamide resins can beused in mixture (“/” represents copolymerization, the same below).

Among the above-described resins, there are more preferably used nylon6, nylon 610 as homopolyamide resins, and copolymer nylon 6/66 thatnylon 6 is copolymerized with other polyamide component as copolyamidesfrom the viewpoints of improving the elongation at break of polyarylenesulfide film and exhibiting the effect of the present invention, inparticular, nylon 610 is preferably used because it has a high effect ofenhancing the elongation at break of polyarylene sulfide film.

The preferable polyetherimide used in the present invention is notparticularly limited as long as it is a polymer having an aliphatic,alicyclic or aromatic ether unit and a cyclic imide group as repeatingunits and having melt moldability. For example, there arepolyetherimides described in U.S. Pat. Nos. 4,141,927, 2,622,678,2,606,912, 2,606,914, 2,596,565, 2,596,566 and 2,598,478; and polymersdescribed in U.S. Pat. Nos. 2,598,536 and 2,599,171, Japanese UnexaminedPatent Publication No. 9-48852, U.S. Pat. Nos. 2,565,556, 2,564,636,2,564,637, 2,563,548, 2,563,547, 2,558,341, 2,558,339 and 2,834,580.Within a range that the effect of the present invention is not damaged,in a main chain of polyetherimide, a structural unit other than cyclicimide and ether imide units, for example, aromatic, aliphatic andalicyclic ester units, an oxycarbonyl unit, etc. may be contained.

In the present invention, a condensate of2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride withm-phenylehediamine or p-phenylenediamine is preferable from theviewpoints of melt moldability. This polyetherimide is available fromGeneral Electric Corporation under a trade name “Ultem” (registeredtrademark).

Regarding the content of the thermoplastic resin (Y) contained in thepolyarylene sulfide film of the present invention, it is preferable thatthe content of polyarylene sulfide is 60 to 99 parts by weight and thecontent of the thermoplastic resin (Y) is 1 to 40 parts by weight whenthe sum of contents of polyarylene sulfide and thermoplastic resin (Y)is 100 parts by weight, from the viewpoints of improving moldingprocessability, acoustic properties and heat moldability. Morepreferably, the thermoplastic resin (Y) is 5 to 30 parts by weight basedon that polyarylene sulfide is 70 to 95 parts by weight, furtherpreferably, the thermoplastic resin (Y) is 7 to 20 parts by weight basedon that polyarylene sulfide is 80 to 93 parts by weight, and mostpreferably, the thermoplastic resin (Y) is 10 to 15 parts by weightbased on that polyarylene sulfide is 85 to 90 parts by weight forobtaining the effect of the present invention. When the thermoplasticresin (Y) is more than 40 parts by weight, excellent heat resistance,etc. of polyarylene sulfide is sometimes deteriorated. Further, when thethermoplastic resin (Y) is less than 1 part by weight, there is a casethat the elongation at break of polyarylene sulfide film of the presentinvention cannot be sufficiently improved, breakage of film occurs inheat molding. Furthermore, there is a case that a demolding propertyfrom a mold after molding and a shape retention property aredeteriorated.

In the present invention, to improve affinity of polyarylene sulfide anda thermoplastic resin (Y), addition of a compatible plasticizer ispreferably adopted. As a specific example of the compatible plasticizer,an alkoxysilane having at least one kind of functional group selectedfrom an epoxy group, an amino group and an isocyanate group ismentioned. As examples of such compound, there are listed epoxygroup-containing alkoxysilane compounds such asγ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane andβ-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; ureido group-containingalkoxysilane compounds such as γ-ureidopropyltriethoxysilane,γ-ureidopropylmethoxysilane andγ-(2-ureidoethyl)aminopropyltrimethoxysilane; isocyanategroup-containing alkoxysilane compounds such asγ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane,γ-isocyanatopropylmethyldimethoxysilane,γ-isocyanatopropylmethyldiethoxysilane,γ-isocyanatopropylethyldimethoxysilane,γ-isocyanatopropylethyldiethoxysilane andγ-isocyanatopropyltrichlorosilane; and amino group-containingalkoxysilane compounds such asγ-(2-aminoethyl)aminopropylmethyldimethoxysilane,γ-(2-aminoethyl)aminopropyltrimethoxysilane andγ-aminopropyltrimethoxysilane. Among them, when an isocyanategroup-containing alkoxysilane compound such asγ-isocyanatepropyltriethoxysilane, γ-isocyanatepropyltrimethoxysilane,γ-isocyanatepropylmethyldimethoxysilane,γ-isocyanatepropylmethyldiethoxysilane,γ-isocyanatepropylethyldimethoxysilane,γ-isocyanatepropylethyldiethoxysilane andγ-isocyanatepropyltrichlorosilane is used, it is preferably used becauseit can improve affinity of polyarylene sulfide and a thermoplastic resin(Y). The added amount of the compatible plasticizer is 0.1 to 10 partsby weight relative to 100 parts by weight in total of polyarylenesulfide and thermoplastic resin (Y), more preferably 0.1 to 5 parts byweight, and further preferably 0.5 to 3 parts by weight.

When using an alkoxysilane having at least one kind of functional groupselected from an epoxy group, an amino group and an isocyanate group, asiloxane bond tends to form between polyarylene sulfide and athermoplastic resin A, and a siloxane bond tends to be present near aninterface of dispersed phase. It is possible to detect a silicon atomnear an interface of dispersed phase by using a TEM-EDX method. In thepresent invention, it is preferable that a silicon (Si) atomconstituting a siloxane bond is contained in an interface of a dispersedphase composed of a thermoplastic resin A.

The polyarylene sulfide film of the present invention is excellent inmolding processability, acoustic properties and heat moldability. Toexhibit such characteristics, it is preferable that polyarylene sulfideconstituting a polyarylene sulfide film forms a sea phase (continuousphase or matrix), and other thermoplastic resin (Y) forms an islandphase (dispersed phase). Further, the average dispersion diameter of thethermoplastic resin (Y) constituting a dispersed phase is preferably0.01 to 2 μm, more preferably 0.02 to 0.5 μm, further preferably 0.05 to0.5 μm, and most preferably 0.05 to 0.3 μm. By which polyarylene sulfideforms a continuous phase, excellent characteristics of polyarylenesulfide such as heat resistance, chemical resistance and electricproperty can greatly reflect on the film. When this average dispersiondiameter is set in the above-described range, it is preferable because apolyarylene sulfide film well balanced in molding processability,acoustic properties and heat moldability is easily obtained. When theaverage dispersion diameter of the dispersed phase is less that 0.01 μm,there is a case that the improvement of molding processability, acousticproperties and heat moldability cannot be sufficiently provided byenhancement of the elongation at break of the present invention.Further, when the average dispersion diameter is more than 2 μm, it isnot preferable because there is a case that heat resistance isdeteriorated and breakage of film occurs upon stretching infilm-forming.

An average dispersion diameter of a dispersed phase herein means anaverage value of diameters in a longitudinal direction, width directionand thickness direction of the film. The average dispersion diameter canbe measured using techniques such as transmission electron microscopeand scanning electron microscope. For example, an average dispersiondiameter can be calculated in such manner that a sample is prepared byan ultra-thin cutting method, the prepared sample is observed using atransmission electron microscope under the condition of applied voltageof 100 kv, and photographed by 10000 magnifications, the pictureobtained is scanned in an image analyzer as an image, and an imagetreatment is conducted by selecting arbitrary 100 of dispersed phases.

The shape of a dispersed phase of the thermoplastic resin (Y) ispreferably spherical, long and thin island, oval or fibrous. Aspectratio of the dispersed phase is preferably in a range of 1 to 30. Afurther preferable range of aspect ratio of the dispersed phase is 2 to20, and a more preferable range is 2 to 10. By setting the aspect ratioof the island component in the above-described range, it is easy toobtain a polyarylene sulfide film excellent in molding processability,improved acoustic properties and heat moldability, and it is preferable.Herein, aspect ratio means a ratio of average major axis/minor axis of adispersed phase. The aspect ratio can be measured using techniques suchas transmission electron microscope and scanning electron microscope.For example, the aspect ratio can be calculated in such manner that asample is prepared by an ultra-thin cutting method, the prepared sampleis observed using a transmission electron microscope under the conditionof applied voltage of 100 kv, and photographed by 10000 magnifications,the picture obtained is scanned in an image analyzer as an image, and animage treatment is conducted by selecting arbitrary 100 of dispersedphases.

Additionally, the average dispersion diameter and aspect ratio ofthermoplastic resin (Y) can be measured as follows, for example.

A sample is prepared by an ultra-thin cutting method by cutting in (i) adirection parallel to a longitudinal direction and perpendicular to filmsurface, (ii) a direction parallel to a width direction andperpendicular to film surface, and (iii) a direction parallel to filmsurface. To make a contrast of a dispersed phase clear, it may also bestained with phosphorus tungsten acid. The cut surface is observed usinga transmission electron microscope (H-7100 FA model manufactured byHitachi Corporation) under the condition of applied voltage of 100 kv,and photographed by 10000 magnifications, the picture obtained isscanned in an image analyzer as an image, and arbitrary 100 of dispersedphases are selected and, if necessary, an image treatment is conducted,thereby to be able to obtain a size of a dispersed phase as follows.There are observed the maximum length (1 a) of the dispersed phaseappeared in the cut surface of (i) in a film thickness direction and themaximum length (1 b) in a longitudinal direction; the maximum length (1c) of the dispersed phase appeared in the cut surface of (ii) in a filmthickness direction and the maximum length (1 d) in a width direction;and the maximum length (1 e) of the dispersed phase appeared in the cutsurface of (iii) in a film thickness direction and the maximum length (1f) in a width direction. Next, when shape index of a dispersed phaseI=(average of 1 b+average of 1 e)/2, shape index J=(average of 1d+average 1 f)/2, and shape index K=(average of 1 a+average 1 c)/2 areset, an average dispersion diameter of the dispersed phase is defined as(I+J+K)/3. Further, from I, J and K, it is determined that the maximumvalue is an average major axis L and the minimum value is an averageminor axis D, and aspect ratio of a dispersed phase is calculated fromL/D.

In the present invention, timing of blending a mixture containingpolyarylene sulfide and a thermoplastic resin (Y) constituting apolyarylene sulfide film is not particularly limited, there are a methodthat before melt extrusion, a mixture of polyarylene sulfide and athermoplastic resin (Y) is previously melt-kneaded (pelletized) forgetting a master chip, and a method that they are mixed and melt kneadedin melt extrusion. Among them, there is preferably exemplified a methodthat they are previously mixed and kneaded using a high shear kneaderproviding a shear stress such as a biaxial extruder for getting a masterchip. In this case, melt film-forming may be done by charging theblended master chip raw material into an ordinary uniaxial extruder, orsheet-forming may be done directly in a state of being provided with ahigh shear without producing a master chip. In the case of mixing by abiaxial extruder, from the viewpoint of reducing a poorly dispersedmaterial, an extruder equipped with a triple biaxial type or doublebiaxial type screw is preferable, in a kneading part, a temperaturerange is preferably a melting point of polyarylene sulfide resin+5 to65° C. A further preferable temperature range is a melting point ofpolyarylene sulfide resin+10 to 45° C. By setting the temperature in akneading part in the preferable range, shear stress is easily heightenedand the effect of reducing a poorly dispersed material can beheightened. The residence time in this case is preferably in a range of1 to 5 minutes. Further, the rotation number of a screw is preferably ina range of 100 to 500 rpm/min, further preferably in a range of 200 to400 rpm/min. By setting the rotation number of a screw in the preferablerange, a high shear stress is easily provided, and the dispersiondiameter of a dispersed phase can be controlled in the preferable rangeof the present invention. Further, ratio (screw axis length/screw axisdiameter) of a biaxial extruder is preferably in a range of 20 to 60,and further preferably in a range of 30 to 50. Furthermore, in a biaxialextruder, in order to heighten a kneading force in a biaxial extruder,it is preferable to provide a kneading part such as kneading paddletherein, a screw shape is constituted by, preferably, the kneading partsof two or more, further preferably three or more. In this case, theorder of blending raw materials is not particularly limited, any methodmay be used, such as a method that all raw materials are compounded andthen melt-kneaded by the above-described method, or a method that a partof raw materials are compounded and then melt-kneaded by theabove-described method, further the other raw material are compoundedand then melt-kneaded, or a method that a part of raw materials arecompounded and then the other raw materials are mixed using a sidefeeder while melt kneading by a uniaxial extruder or biaxial extruder.Further, there can be preferably exemplified a method using asupercritical fluid described in journal of Japan Society PlasticProcessing, “Processing” vol. 15 (6), p. 382-385 (2003).

In the polyarylene sulfide film of the present invention, in order toobtain heat moldability of the present invention, it is preferable thatan inert particle is contained by 0.1 to 30 parts by weight relative to100 parts by weight in total of polymers constituting the film. The heatmoldability of the present invention means that a film can be processedwithout generating breakage of film in heat molding and afterprocessing, demolding property from a mold is excellent and film formretention property of the film taken out is excellent. When the contentof inert particle is less than 0.1 parts by weight relative to 100 partsby weight of the whole polymer, breakage of film hardly occurs in heatmolding, but demolding property from a mold and film retention propertyare sometimes deteriorated. When the content of inert particle is morethan 30 parts by weight relative to 100 parts by weight of the wholepolymer, the elongation at break of film is sometimes lowered andbreakage of film sometimes occurs in heat molding. The content of inertparticle is more preferably 0.6 to 30 parts by weight, furtherpreferably 1 to 20 parts by weight, and most preferably 5 to 20 parts byweight.

As the inert particle used in the present invention, there are listedinorganic particles such as calcium carbonate, silica, titanium oxide,alumina, kaolin, calcium phosphate, barium sulfate, talc and zinc oxide,and organic particles not melting till 300° C. such as crosslinkedstyrene based particle. Calcium carbonate and silica are preferable, andthese particles are preferable because they are good in affinity topolymers and hardly generate void near particles in film-forming.

The particle diameter of an inert particle used in the present inventionis preferably 0.1 μm or more and 3 μm or less, more preferably 0.5 to1.5 μm. When the particle diameter is less than 0.1 μm, demoldingproperty from a mold and film retention property after heat molding ofthe present invention are sometimes deteriorated. When more than 3 μm,the elongation at break of film is sometimes lowered, and breakage offilm sometimes occurs in heat molding.

In the present invention, timing of blending polyarylene sulfide and aninert particle constituting a polyarylene sulfide film is notparticularly limited, there is preferably used a method that before meltextrusion, a mixture of polyarylene sulfide and an inert particle ispreviously melt-kneaded (pelletized) for getting a master chip. Amongthem, there is preferably exemplified a method that they are previouslykneaded using a high shear kneader providing a shear stress such as abiaxial extruder for getting a master chip. In the case of mixing by abiaxial extruder, from the viewpoint of reducing a poorly dispersedmaterial, an extruder equipped with a triple biaxial type or doublebiaxial type screw is preferable. Further, the rotation number of ascrew is preferably 100 to 500 rpm/min, further preferably in a rage of200 to 400 rpm/min. By setting the rotation number of a screw in thepreferable range, a high shear stress is easily provided, and dispersionof particle can be improved. Further, ratio (screw axis length/screwaxis diameter) of a biaxial extruder is preferably in a range of 20 to60, and further preferably in a range of 30 to 50.

In the polyarylene sulfide film of the present invention, it ispreferable that the Young's modulus thereof at 120° C. is 0.6 GPa ormore and 2 GPa or less, more preferably 0.8 GPa or more and 2 GPa orless to improve heat moldability of the present invention. When theYoung's modulus is less than 0.6 GPa, demolding property after heatmolding is sometimes deteriorated, when the Young's modulus is more than2 GPa, it is necessary to make a draw ratio in film-forming extremelyhigh, the elongation at break of a film is sometimes lowered, andbreakage of film sometimes generates in heat molding. Herein, Young'smodulus of a film at 120° C. represents an average in a longitudinaldirection and a width direction.

In the polyarylene sulfide film of the present invention, it ispreferable that the elongation at break of a film at 120° C. ispreferably 100% or more and 250% or less, more preferably 130% or moreand 230% or less, and further preferably 150% or more and 200% or less.Herein, elongation at break of a film at 120° C. represents an averagein a longitudinal direction and a width direction.

In order to set the Young's modulus and elongation at break of a film at120° C. in the range of the present invention, this can be achieved insuch manner that the thermoplastic resin and inert particle of thepresent invention are added by the present specific range, and the drawratio in a longitudinal direction and a width direction upon productionof the film of the present invention is set in a range of 2.4 to 4,preferably 2.6 to 3.6, and further preferable 2.6 to 3.4. Further,heat-set of this stretched film under extension or relaxing in a widthdirection tends to obtain the effect of the present invention.

The density of the polyarylene sulfide film of the present invention is,from the viewpoint of improving acoustic properties, preferably 1.3g/cm³ or more and 1.4 g/cm³ or less, more preferably 1.32 g/cm³ or moreand 1.39 g/cm³ or less, and further preferably 1.33 g/cm³ or more and1.38 g/cm³ or less. When the density is less than 1.3 g/cm³, it is notpreferable because an effect of improving acoustic properties is hardlyobtained sometimes. On the other hand, when the density is more than 1.4g/cm³, it is not preferable because breakage of film often occurs infilm-forming. In order to set the density of a film in the preferablerange of the present invention, the heat-set temperature after biaxialstretching is set in a range of 200 to 275° C., preferably 220 to 270°C., and further preferably 240 to 265° C. Further, the heat-set time ispreferably set in a range of 0.2 to 30 seconds.

In the polyarylene sulfide film for an acoustic instrument vibratingplate of the present invention, the thickness of film is preferably 3 μmor more and 100 μm or less, more preferably 10 μm or more and 100 μm orless, further preferably 15 μm or more and 75 μm or less, and mostpreferably 20 μm or more and 60 μm or less. When the thickness of filmis less than 3 μm, it is not preferable because the film easily deformsin handling, handling the film becomes difficult. On the other hand,when the thickness of film exceeds 100 μm, it is not preferable becauselow-pass reproduction becomes insufficient, there tends to arise aproblem that peak-dip on acoustic frequency characteristics easilyoccurs and so on.

In the polyarylene sulfide film of the present invention, within a rangethat the effect of the present invention is not damaged, othercomponents may be added such as a heat stabilizer, antioxidant,ultraviolet absorber, antistatic agent, flame retardant, pigment, dye,and organic lubricant including fatty acid ester and wax. Further, inorder to provide a film surface with easy lubrication, abrasionresistance, scratch resistance and the like, inorganic and organicparticles can be also added in a polyarylene sulfide film. As theadditives, for example, there are listed inorganic particles such asclay, mica, titanium oxide, calcium carbonate, kaolin, talc, wet or drysilica, colloidal silica, calcium phosphate, barium sulfate, alumina andzirconia; and organic particles having constitutional components such asacrylic acids and styrene; so-called internal particles precipitated bycatalysts, etc. being added in polymerization reaction of polyphenylenesulfide; and surfactants.

Further, if necessary, the polyarylene sulfide film of the presentinvention may be subjected to an arbitrary processing such as heattreatment, forming, surface treatment, lamination, coating, printing,emboss treatment and etching.

The polyarylene sulfide film of the present invention is preferably forheat molding. The heat-forming temperature is preferably the glasstransition temperature of polyphenylene sulfide or higher, morepreferably the glass transition temperature of polyphenylene sulfide+50°C. or more, and further preferably the glass transition temperature ofpolyphenylene sulfide+100° C. or more. By heat molding in the range,breakage of film can be suppressed in molding.

Further, whereas a glass transition temperature (Tg) of the polyarylenesulfide film of the present invention is observed at 85° C. or more andless than 95° C., it is preferably not observed at 95° C. or more to130° C. or less. When Tg is less than 85° C., heat resistance of filmsometimes becomes low, and when Tg is observed at 95° C. or more to 130°C. or less, breakage of film sometimes occurs in heat molding.

Next, methods for forming the polyarylene sulfide film of the presentinvention will be described with reference to a production of biaxiallyoriented polyphenylene sulfide film constituted by a mixed phasecontaining poly(p-phenylene)sulfide as polyarylene sulfide and polyamideas a thermoplastic resin (Y). Apparently, the present invention is notlimited to the following descriptions.

In the case where polyphenylene sulfide and nylon 610 are mixed, thereis preferably exemplified a method that a mixture of respective resinsis previously melt-kneaded (pelletized) for getting a master chip beforemelt extrusion.

In the present invention, first, the above-described PPS and nylon 610are charged in a biaxial kneading extruder, it is preferable to produceblend raw materials having a weight ratio of PPS and nylon 610 of 99/1to 60/40. The method for mixing/kneading a resin composition of blendraw materials is not particularly limited, various mixing/kneading meansare used. For example, each may be separately fed to a melt extruder andmixed, or only powder raw materials may be previously dry-blended byutilizing a mixing machine such as Henschel mixer, ball mixer, blenderand tumbler, thereafter, melt-kneaded by a melt kneader. It ispreferable from the viewpoints of film quality and film-formingperformance that thereafter, if necessary, the above-described blend rawmaterials is charged to an extruder together with PPS and recovered rawmaterials thereof to produce a target composition as a raw material. Inthe case of producing the above-described raw material, in order toprevent foreign materials mixing in a film to the utmost extent,filtration of resins can be preferably conducted in a melt extrusionstep. In order to remove foreign materials and degrade polymers in thisextruder, it is preferable to use various filters, for examples, filtersmade of sintered metal, porous ceramic, sand and metal net. Further, ifnecessary, a gear pump may be equipped to improve quantitative feedperformance.

More specific conditions of a method for producing the above-describedpreferable polyphenylene sulfide film are as follows.

First, pellets or granules of polyphenylene sulfide and pellets of nylon610 are mixed in a constant ratio, fed to a vent type biaxial kneadingextruder and melt-kneaded to give a blend chip. It is preferable to usea high-shear mixer providing shear stress such as a biaxial extruder,further, from the viewpoints of reducing a poorly dispersed material,one equipped with a triple biaxial type or double biaxial type screw ispreferable and the residence time in this case is preferably 1 to 5minutes. Further, a resin temperature in a kneading part is preferablyin a range of the melting point of polyarylene sulfide resin+5 to 65°C., a more preferable temperature range is the melting point ofpolyarylene sulfide resin+10 to 45° C. By setting the resin temperaturein a kneading part in the preferable range, shear stress is easilyheightened, an effect of reducing a poorly dispersed material becomeshigh, and dispersion diameter of a dispersed phase can be controlled inthe preferable range of the present invention. Further, the rotationnumber of a screw is preferably 100 to 500 rpm/min, further preferablyin a rage of 200 to 400 rpm/min. By setting the rotation number of ascrew in the preferable range, a high shear stress is easily provided,and the dispersion diameter of a dispersed phase can be controlled inthe preferable range of the present invention. Further, ratio (screwaxis length/screw axis diameter) of a biaxial extruder is preferably ina range of 20 to 60, and further preferably in a range of 30 to 50.Furthermore, in order to heighten a kneading force in a biaxialextruder, it is preferable to provide a kneading part such as kneadingpaddle therein, it is further preferable that a screw shape isconstituted by providing two or more of the kneading parts to be anordinary feed screw between respective kneading parts.

In blending polyphenylene sulfide and nylon 610, when a blendcomposition of polyphenylene sulfide and nylon 610 or a compatibleplasticizer is added, a poorly dispersed material can be sometimesreduced and compatibility is sometimes heightened.

Thereafter, a blend chip composed of PPS and nylon 610 obtained by theabove-described pelletizing operation, and optionally a raw materialthat PPS and a recovered raw material or particle after film-forming areblended are suitably mixed in a constant ratio, dried at 180° C. underreduced pressure for 3 hours or more, and then charged in an extruderheated at a temperature of 300 to 350° C., preferably 320 to 340° C.Thereafter, a melt polymer via the extruder is passed through a filter,and the melt polymer is then extruded into a sheet form using a T-die.This sheet-like material is closely contacted on a cooling drum at itssurface temperature of 20 to 70° C., cooled and solidified, thereby togive an unstretched polyphenylene sulfide film in a substantiallyunoriented state.

Next, this unoriented polyphenylene sulfide film is biaxially stretchedto give a biaxial orientation. As a stretching method, there can be useda sequential biaxial stretching method (stretching method in combinationof stretching in each direction such as a method of stretching in awidth direction after stretching in a longitudinal direction), asimultaneous biaxial stretching method (method of simultaneouslystretching in longitudinal and width directions) or a method incombination thereof.

Herein, there is used a sequential biaxial stretching method thatstretching is first done in a longitudinal direction and next in a widthdirection. The stretching temperature varies depending on constitutionalcomponents of PPS and polyamide constituting a film, for example, itwill be explained below by an example of a resin composition composed of90 parts by weight of PPS and 10 parts by weight of nylon 610.

Unoriented polyphenylene sulfide film is heated by a group of heatrolls, the draw ratio is 2.2 to 5 in a longitudinal direction (MDdirection), preferably 2.4 to 4.5, and further preferably 2.6 to 4,being stretched in one step or multi-step more than one step (MDstretching) from the viewpoints of setting the elongation at break andYoung's modulus in the preferable range of the present invention. Thestretching temperature is in a range of Tg (glass transition temperatureof PPS) to (Tg+50)° C., preferably (Tg+5) to (Tg+50)° C., and furtherpreferably (Tg+5) to (Tg+40)° C. Thereafter, it is cooled by a group ofcooling rolls at 20 to 50° C.

As a stretching method in a width direction (TD direction) following byMD stretching, for example, a method using a tenter is common. This filmis introduced to a tenter while holding both the ends by clips, andstretched in a width direction (TD stretching). The stretchingtemperature is preferably from Tg to (Tg+60)° C., more preferably (Tg+5)to (Tg+50)° C., and further preferably (Tg+10) to (Tg+40)° C. From theviewpoints of setting the elongation at break and Young's modulus in thepreferable range of the present invention, the draw ratio is 2.2 to 5,preferably 2.4 to 4.5, and further preferably 2.6 to 4.

Next, this stretched film is heat-set under extension or relaxing in awidth direction. A preferable heat-set temperature is in a range of 200to 275° C., more preferably 220 to 270° C., and further preferably 240to 265° C. The heat-set time is preferably set in a range of 0.2 to 30seconds. Further, this film is cooled in a temperature zone of 40 to180° C. while relaxing in a width direction. The relaxing rate is, fromthe viewpoint of improving the elongation at break, preferably in arange of 1 to 10%, more preferably 2 to 9%, and further preferably 3 to8%.

Further, the film is, if necessary, While conducting a relaxingtreatment in longitudinal and width directions, cooled to roomtemperature and wound up to give a target biaxially orientedpolyphenylene sulfide film.

Next, a method for producing the polyarylene sulfide film of the presentinvention will be described, using calcium carbonate of 1.2 μm particlediameter as an inert particle, by an example of production of abiaxially oriented polyphenylene sulfide film constituted by a mixedlayer containing poly-p-phenylene sulfide (sometimes abbreviated as PPS)as polyarylene sulfide and polyetherimide as a thermoplastic resin (Y).Apparently, the present invention is not limited to the followingdescriptions.

In the case of blending polyphenylene sulfide, calcium carbonate andpolyetherimide, there is preferably exemplified a method that, beforemelt extrusion, a mixture of respective resins is previouslymelt-kneaded beforehand (pelletized) for getting a master chip.

In the present invention, first, a master raw material of PPS andcalcium carbonate is produced. PPS and calcium carbonate are charged ina biaxial kneading extruder, and a master raw material having a weightratio of 95/5 to 70/30 is produced. Mixing/kneading method is notparticularly limited, various mixing/kneading means are used. Forexample, it may be mixed using a mixing machine such as Henschel mixer,ball mixer, blender and tumbler, thereafter, melt-kneaded by a meltkneader.

Next, a blend raw material of PPS and polyetherimide is produced. PPSand polyetherimide are charged in a biaxial kneading extruder, it ispreferable to produce a blend raw material for a weight ratio of PPS andpolyetherimide to be 99/1 to 50/50. Mixing/kneading method of a resincomposition of blend raw materials is not particularly limited, variousmixing/kneading means are used. For example, each may be separately fedto a melt extruder and mixed, or only powder raw materials may bepreviously dry-blended by utilizing a mixing machine such as Henschelmixer, ball mixer, blender and tumbler, thereafter, melt-kneaded by amelt kneader.

In kneading PPS and calcium carbonate, or PPS and polyetherimide, eachis fed to a vent type biaxial kneading extruder and melt-kneaded to givea blend chip. It is preferable to use a high-shear mixer providing shearstress such as a biaxial extruder, further, from the viewpoints ofreducing a poorly dispersed material, one equipped with a triple biaxialtype or double biaxial type screw is preferable and the residence timeis in this case preferably 1 to 5 minutes. Further, a resin temperaturein a kneading part is preferably in a range of the melting point ofpolyarylene sulfide resin+5 to 65° C. A further preferable temperaturerange is the melting point of polyarylene sulfide resin+10 to 45° C. Bysetting the resin temperature in a kneading part in the preferablerange, shear stress is easily heightened, an effect of reducing a poorlydispersed material becomes high, and dispersion diameter of a dispersedphase can be controlled in the preferable range of the presentinvention. Further, the rotation number of a screw is preferably 100 to500 rpm/min, further preferably in a rage of 200 to 400 rpm/min.Further, ratio (screw axis length/screw axis diameter) of a biaxialextruder is preferably in a range of 20 to 60, and further preferably ina range of 30 to 50. Furthermore, in order to heighten a kneading forcein a biaxial extruder, it is preferable to provide a kneading part suchas kneading paddle therein, it is further preferable that a screw shapeis constituted by providing two or more of the kneading parts to be anordinary feed screw between respective kneading parts.

In blending PPS and polyetherimide, when a compatible plasticizer isadded, a poorly dispersed material can be sometimes reduced andcompatibility is sometimes heightened.

Next, a raw material that a master raw material of PPS and calciumcarbonate, a blend raw material composed of PPS and polyetherimideobtained by the above-described pelletizing operation, and optionallyPPS and a recovered raw material or particle after film-forming areblended is suitably mixed in a constant ratio, dried at 180° C. underreduced pressure for 3 hours or more, and then charged in an extruderheated at a temperature of 300 to 350° C., preferably 320 to 340° C.Thereafter, a melt polymer via the extruder is passed through a filter,and the melt polymer is then extruded into a sheet form using a T-die.This sheet-like material is closely contacted on a cooling drum at itssurface temperature of 20 to 70° C., cooled and solidified, thereby togive an unstretched polyphenylene sulfide film in a substantiallyunoriented state.

Next, this unoriented polyphenylene sulfide is biaxially stretched togive a biaxial orientation. As a stretching method, there can be used asequential biaxial stretching method (stretching method in combinationof stretching in each direction such as a method of stretching in awidth direction after stretching in a longitudinal direction), asimultaneous biaxial stretching method (method of simultaneouslystretching in longitudinal and width directions) or a method incombination thereof. Herein, there is used a sequential biaxialstretching method that stretching is first done in a longitudinaldirection and next in a width direction. The stretching temperaturevaries depending on constitutional components of PPS and polyetherimideconstituting a film, for example, it will be explained below by anexample of a resin composition composed of 80% by weight of PPS, 10% byweight of calcium carbonate and 10% by weight of polyetherimide.

Unoriented polyphenylene sulfide film is heated by a group of heatrolls, and stretched in a longitudinal direction (MD direction) with adraw ratio of 2.4 to 4, preferably 2.6 to 3.6, and further preferably2.6 to 3.4 by one step or multi-step more than one step (MD stretching).The stretching temperature is in a range of Tg (glass transitiontemperature of PPS) to (Tg+50)° C., preferably (Tg+5) to (Tg+50)° C.,and further preferably (Tg+5) to (Tg+40)° C. Thereafter, it is cooled bya group of cooling rolls at 20 to 50° C.

As a stretching method in a width direction (TD direction) following MDstretching, for example, a method using a tenter is common. This film isintroduced to a tenter while holding both the ends by clips, stretchedin a width direction (TD stretching). The stretching temperature ispreferably from Tg to (Tg+60)° C., more preferably (Tg+5) to (Tg+50)°C., and further preferably (Tg+10) to (Tg+40)° C. The draw ratio is 2.4to 4, more preferably 2.6 to 3.6, and further preferably 2.6 to 3.4.

Next, this stretched film is heat-set under extension or relaxing in awidth direction. A preferable heat-set temperature is in a range of 200to 275° C., more preferably 220 to 270° C., and further preferably 240to 265° C. The heat-set time is preferably set to a range of 0.2 to 30seconds. Further, this film is cooled in a temperature zone of 40 to180° C. while relaxing in a width direction. The relaxing rate is, fromthe viewpoint of improving the elongation at break, preferably in arange of 1 to 10%, more preferably 1 to 8%, and further preferably 1 to5%.

Further, the film is, if necessary, while conducting a relaxingtreatment in longitudinal and width directions, cooled to roomtemperature and wound up to give a target biaxially orientedpolyphenylene sulfide film.

[Measuring Method of Physical Property and Evaluation Method of Effect](1) Elongation at Break, Young's Modulus (Room Temperature)

A film was cut in the longitudinal and width directions to a strip-likesample of 200 mm in length and 10 mm in width and used. Elongation atbreak and Young's modulus were measured in accordance with JIS K7127 andJIS Z1702, respectively using a tensile tester of Instron type. Themeasurement was conducted in the following conditions, 10 samples weremeasured each in MD direction and TD direction and the average wasobtained. Measuring apparatus: “Tensilon AMF/RTA-100”, automatic filmstress-strain tester manufactured by Orientec Corporation Sample size:10 mm in width×100 mm in length of sample Tensile speed: 100 mm/min

Measuring environment: temperature 23° C., humidity 65% RH

(2) Elongation at Break, Young's Modulus (120° C.)

A film was cut in the longitudinal and width directions to a strip-likesample of 200 mm in length and 10 mm in width and used. Elongation atbreak and Young's modulus were measured in accordance with JIS K7127 andJIS Z1702, respectively using a tensile tester of Instron type. Themeasurement was conducted in the following conditions, 10 samples weremeasured each in MD direction and TD direction and the average wasobtained. Measuring apparatus: “Tensilon AMF/RTA-100”, automatic filmstress-strain tester manufactured by Orientec Corporation Sample size:10 mm in width×100 mm in length of sample Tensile speed: 100 mm/min

Measuring environment: temperature 120° C.

(3) Film Thickness

Film thickness was measured at 23° C., 65% RH by a needle pressure of 30g using an electric micrometer (K-312A model) manufactured by AnritsuCorporation.

(4) Detection of Silicon Atom in Interface of Dispersion Diameter

A film was cut parallel to a longitudinal direction and perpendicular tofilm surface, and a sample was prepared by an ultra-thin cutting method.In order to make a contrast of a dispersed phase clear, it may bestained with osmic acid, ruthenium acid or phosphorus tungsten acid.When a thermoplastic resin A is polyamide, phosphorus tungsten acid ispreferably used for dyeing. The cut surface was measured using a fieldemission type electron microscope (JEM2100F manufactured by JEOL Corp.,EDX (JED-2300T manufactured by JEOL Corp.)) in the conditions: appliedvoltage of 200 kv, sample absorption current of 10⁻⁹A, EDX-ray analysis20 sec/point and beam diameter of 1 nm by a TEM-EDX method, to evaluatean interface of a dispersed phase. Ten arbitrary dispersed phases wereevaluated, one which was detectable was o and one which was notdetectable was x.

(5) Molding Processability 1

A film is heated in an temperature atmosphere of 150° C., pressed at apressure of 0.4 MPa for 15 seconds in a mold which is heated at about230° C. and has a deep drawing part capable of bending a film at 180°,cooled to 150° C., and then taken out at room temperature to produce anacoustic instrument vibrating plate (FIG. 1) used in a speaker with aconstitution shown in FIG. 2. A diameter of coil is set to 10 mm. Inthis case, 100 pieces of speakers were produced, processability wasevaluated in the following criteria. ⊚, ∘ are accepted.

⊚: No problem at all, film can be formed in a desired shape.∘: 1 to 3 pieces, wrinkle occurs due to heat shrinkage strain.Δ: 4 to 7 pieces, wrinkle occurs due to heat shrinkage strain.x: 8 pieces or more, wrinkle occurs due to heat shrinkage strain, filmis torn in processing and vibrating plate with a desired shape can notobtained.

(6) Heat Resistance

A vibrating plate formed in a desired shape is left in an atmosphere at100° C. Thereafter, the vibrating plate is taken out at room temperatureto observe degree of heat deformation. The heat resistance was evaluatedby the following criteria. ⊚, ∘ are accepted.

⊚: No heat deformation at all, shape after forming is maintained as itis.∘: Some heat deformation, but shape after forming is almost maintained.x: Vibrating plate is strained as whole with deep-drawing part andfolding part being stretched and deformed.

(7) Acoustic Property

Evaluation was done by measuring frequency property in accordance withJIS C 5532, when there is no fluttering sound, and high sound pressurein low tone range with being very excellent as speaker is shown as ⊚.Good as speaker is shown as ∘, and when fluttering sound generates, poorperformance is shown as x. ⊚, ∘ are accepted.

(8) Molding Processability 2, Demolding Property after Molding, andShape Retention Property

A film is pressed at a pressure of 0.4 MPa for 15 seconds in a moldwhich is heated at 180° C. or 230° C. and has a deep drawing partcapable of bending a film at 180°, cooled to 100° C. or 120° C., andthen taken out at room temperature to evaluate heat moldability,demolding property after molding and shape retention property by thefollowing criteria.

(Heat Moldability)

∘: Film can be molded without breakage of film.x: Film is torn in molding, vibrating plate with a desired shape is notobtained.

(Demolding Property and Shape Retention Property)

∘: Film can be taken out from a mold, desired shape after being takenout is maintained.x: Film is hardly taken out from a mold, shape after being taken out isdeformed.

EXAMPLES Reference Example 1 Polymerization of poly-p-phenylene sulfide(PPS)

In an autoclave of 70 liters equipped with a stirrer, discharged were8,267.37 g of 47.5 wt % sodium hydrosulfide (70.00 mol), 2,957.21 g of96 wt % sodium hydroxide (70.97 mol), 11,434.50 g ofN-methyl-2-pyrrolidone (NMP) (115.50 mol), 2,583.00 g of sodium acetate(31.50 mol) and 10, 500 g of ion-exchanged water, slowly heated to 245°C. over about 3 hours at normal pressure while passing nitrogen, after14, 780.1 g of water and 280 g of NMP were distilled away, the reactioncontainer was cooled to 160° C. The remaining water content inside thesystem per 1 mol of alkali metal sulfide charged was 1.06 moles togetherwith water consumed by hydrolysis of NMP. Further, the amount ofhydrogen sulfide flied out was 0.02 moles per 1 mol of alkali metalsulfide charged.

Next, 10,235.46 g of p-dichlorobenzene (69.63 mol) and 9,009.00 g of NMP(91.00 mol) were added, the reaction container was sealed under nitrogengas, while stirring at 240 rpm, raised to 238° C. at a speed of 0.6°C./min. After conducting reaction at 238° C. for 95 minutes, thetemperature was raised to 270° C. at a speed of 0.8° C./min. Afterconducting reaction at 270° C. for 100 minutes, while injecting 1,260 g(70 mol) of water therein over 15 minutes, cooled to 250° C. at a speedof 1.3° C./min. Thereafter, it was cooled to 200° C. at a speed of 1.0°C./min, then rapidly cooled near room temperature.

The content was taken out, diluted with 26,300 g of NMP, then thesolvent and solid content were filtered by a sieve (80 mesh), and theresulting particle was washed with 31,900 g of NMP and collected byfiltration. This was washed several times with 56,000 g of ion-exchangedwater and collected by filtration, then washed with 70,000 g of 0.05 wt% acetic acid aqueous solution and collected by filtration. Afterwashing with 70,000 g of ion-exchanged water and collecting byfiltration, the resulting PPS particle was dried by hot air at 80° C.,and dried under reduced pressure at 120° C. The thus obtained PPS had amelt viscosity of 200 Pa·s (310° C., shear velocity 1,000/s), the glasstransition temperature was 90° C., and the melting point was 285° C.

Reference Example 2 Production of Nylon 6/66 Copolymer (polyamide-3(PA-3))

50 wt % aqueous solution of salt (AH salt) of adipic acid withhexamethylenediamine, and ∈-caprolactam (CL) were mixed so that AH saltwas 20 parts by weight and CL was 80 parts by weight, and the mixturewas charged in an autoclave of 30 liters. After it was raised to 270° C.at an internal pressure of 10 kg/cm², the internal temperature wasmaintained at 245° C., while stirring, the pressure was slowly reducedto 0.5 kg/cm² and stirring was stopped. After being returned to normalpressure by nitrogen, a strand was drawn out, pelletized, and unreactedsubstances were extracted out using boiling water, and dried. The thusobtained copolyamide 6/66 resin had a relative viscosity of 4.20 andmelting point of 193° C.

Reference Example 3 Production of Polyethylene-2,6-Naphthalate (PEN)Polymer Chip

To a mixture of 100 parts by weight of dimethyl 2,6-naphthalate and 60parts by weight of ethylene glycol, 0.03 parts by weight of manganeseacetate tetrahydrate was added, and ester exchange reaction wasconducted while the temperature was slowly raised from 150° C. to 240°C. Along the way, when the reaction temperature reached at 170° C.,0.024 parts by weight of antimony trioxide was added thereto. Further,when the reaction temperature reached at 220° C., 0.042 parts by weightof tetrabutyl 3,5-dicarboxybenzenesulfonate phosphonium salt(corresponding to 2 mmol %) was added thereto. Thereafter, the esterexchange reaction was continuously conducted, after completion of esterexchange reaction, 0.023 parts by weight of trimethyl phosphate wasadded thereto. Next, the reaction product was transferred to apolymerization reactor, the temperature was raised to 290° C.,polycondensation reaction was conducted under a highly reduced pressureof 0.2 mmHg or less, thereby to give a polyethylene-2,6-naphthalate chiphaving an inherent viscosity of 0.65 dl/g.

Example 1

A raw material that 0.3 wt % of calcium carbonate powder having anaverage particle diameter of 1.2 μm and 0.05 wt % of calcium stearatewere added to 100 parts by weight of the PPS resin produced in Referenceexample 1 and uniformly dispersed/compounded raw material was dried at150° C. under reduced pressure for 3 hours, and then fed to a uniaxialextruder of full-flight that the melt part was heated at 320° C. Next,the polymer melted by the extruder was filtered trough a filter whosetemperature was set at 320° C., melt-extruded from a T-die set at 320°C., and then closely contacted on a cast drum of surface temperature at25° C. while applying static charge thereon to be cooled and solidified,thereby to produce an unstretched polyphenylene sulfide film.

This unstretched polyphenylene sulfide film was stretched at 107° C. by3.3 times in a longitudinal direction of film by using a longitudinalstretch machine constituted by a plurality of rolls heated and byutilizing circumferential velocity difference between rolls. Thereafter,this film was introduced to a tenter while holding both ends by clips,stretched at a draw temperature of 107° C. by a draw ratio of 3.3 in awidth direction of film, followed by heat treatment at a temperature of265° C. for 4 seconds, then subjected to a 5% relaxing treatment in alateral direction in a cool zone controlled at 150° C., cooled to roomtemperature, and the film edges were removed, thereby to produce abiaxially oriented polyphenylene sulfide film of 30 μm in thickness.

The measurement and evaluation results on the constitution andcharacteristic of the biaxially oriented polyphenylene sulfide filmobtained are shown in Table 1, and this biaxially oriented polyphenylenesulfide film was excellent in molding processability, heat resistanceand acoustic properties.

Example 2

A biaxially oriented polyphenylene sulfide film was obtained in the samemanner as in Example 1 except that the draw ratio in the film-formingcondition of biaxially oriented polyphenylene sulfide film was changedas shown in Table 1. The biaxially oriented polyphenylene sulfide filmobtained in the present Example was excellent in molding processability,heat resistance and acoustic properties.

Example 3

PPS resin produced in Reference example 1 of 90 parts by weight wasdried at 180° C. under reduced pressure for 3 hours, as a thermoplasticresin (Y), nylon 610 resin (nylon resin, “Amilan CM2001” manufactured byToray Industries Inc., polyamide-1 (PA-1)) of 10 parts by weight wasdried at 120° C. under reduced pressure for 3 hours, further, as acompatible plasticizer, γ-isocyanatepropyltriethoxysilane (“KBE9007”manufactured by Shin-Etsu Chemical Co., Ltd.) of 0.5 parts by weight wascompounded to 100 parts by weight in total of the PPS resin and nylon610, then charged in a co-rotational biaxial kneading extruder having avent provided with three kneading paddle mixing parts being heated at330° C. (manufactured by Japan Steel Works Ltd., screw diameter 30 mm,screw length/screw diameter=45.5), and melt extruded in a strand form byresidence time of 90 seconds and screw rotation number of 300 rpm/min,cooled in water at 25° C., then immediately cut to produce a blend chip.A raw material that 0.3 wt % of calcium carbonate powder having anaverage particle diameter of 1.2 μm and 0.05 wt % of calcium stearatewere added to 100 parts by weight of the blend chip of PPS/PA-1 (90/10wt %) and uniformly dispersed/compounded raw material was dried at 150°C. under reduced pressure for 3 hours, and then fed to a uniaxialextruder of full-flight that the melt part was heated at 320° C.

Next, the polymer melted by the extruder was filtered trough a filterwhose temperature was set at 320° C., melt-extruded from a T-die set at320° C., and then closely contacted on a cast drum of surfacetemperature at 25° C. while applying static charge thereon to be cooledand solidified, thereby to produce an unstretched polyphenylene sulfidefilm.

This unstretched polyphenylene sulfide film was stretched at 110° C. by2.8 times in a longitudinal direction of film by using a longitudinalstretch machine constituted by a plurality of rolls heated and byutilizing circumferential velocity difference between rolls. Thereafter,this film was introduced to a tenter while holding both ends by clips,stretched at a draw temperature of 110° C. by a draw ratio of 2.8 in awidth direction of film, followed by heat treatment at a temperature of265° C. for 4 seconds, then subjected to a 5% relaxing treatment in alateral direction in a cool zone controlled at 150° C., cooled to roomtemperature, and the film edges were removed, thereby to produce abiaxially oriented polyphenylene sulfide film of 30 μm in thickness.

The measurement and evaluation results on the constitution andcharacteristic of the biaxially oriented polyphenylene sulfide filmobtained are shown in Table 1, and this biaxially oriented polyphenylenesulfide film was excellent in molding processability, heat resistanceand acoustic properties.

Examples 4, 5, 6

A biaxially oriented polyphenylene sulfide film was obtained in the samemanner as in Example 3 except that the added amount of PA-1 as athermoplastic resin (Y) was changed as shown in Table 1. The measurementand evaluation results on the constitution and characteristic of thebiaxially oriented polyphenylene sulfide film obtained were shown inTable 1. The biaxially oriented polyphenylene sulfide film obtained inExample 4 was excellent in molding processability, heat resistance andacoustic properties. The biaxially oriented polyphenylene sulfide filmobtained in Example 5 was somewhat inferior in heat resistance, but wasa level usable in practice, was excellent in processability and acousticproperties. The biaxially oriented polyphenylene sulfide film obtainedin Example 6 was somewhat inferior in molding processability, but was alevel usable in practice, was excellent in heat resistance and acousticproperties.

Example 7

A biaxially oriented polyphenylene sulfide film was obtained in the samemanner as in Example 3 except that as a thermoplastic resin (Y), nylon 6(CM1001 manufactured by Toray Industries Inc., polyamide-2 (PA-2)) wasused. The measurement and evaluation results on the constitution andcharacteristic of the biaxially oriented polyphenylene sulfide filmobtained are shown in Table 1, and the biaxially oriented polyphenylenesulfide film obtained in the present Example was excellent in moldingprocessability, heat resistance and acoustic properties.

Example 8

A biaxially oriented polyphenylene sulfide film was obtained in the samemanner as in Example 3 except that as a thermoplastic resin (Y), nylon6/66 copolymer (polyamide-3 (PA-3)) prepared in Reference example 2 wasused. The measurement and evaluation results on the constitution andcharacteristic of the biaxially oriented polyphenylene sulfide filmobtained are shown in Table 1, and the biaxially oriented polyphenylenesulfide film obtained in the present Example was excellent in moldingprocessability, heat resistance and acoustic properties.

Example 9

A biaxially oriented polyphenylene sulfide film was obtained in the samemanner as in Example 3 except that as a thermoplastic resin (Y),polyetherimide (“Ultem 1010” manufactured by GE Plastics Corporation)(PEI) was used. The measurement and evaluation results on theconstitution and characteristic of the biaxially oriented polyphenylenesulfide film obtained are shown in Table 1, and the biaxially orientedpolyphenylene sulfide film obtained in the present Example was excellentin molding processability, heat resistance and acoustic properties.

Examples 10, 11

A biaxially oriented polyphenylene sulfide film was obtained in the samemanner as in Example 3 except that the added amount of PEI as athermoplastic resin (Y) was changed as shown in Table 1. The measurementand evaluation results on the constitution and characteristic of thebiaxially oriented polyphenylene sulfide film obtained were shown inTable 1. The biaxially oriented polyphenylene sulfide film obtained inExample 10 was excellent in molding processability, heat resistance andacoustic properties. The biaxially oriented polyphenylene sulfide filmobtained in Example 11 was somewhat inferior in molding processability,heat resistance and acoustic properties, but was a level usable inpractice.

Example 12

A biaxially oriented polyphenylene sulfide film was obtained in the samemanner as in Example 9 except that the draw ratio in the film-formingcondition of biaxially oriented polyphenylene sulfide film obtained inExample 9 was changed as shown in Table 1. The biaxially orientedpolyphenylene sulfide film obtained was somewhat inferior in moldingprocessability, but was excellent in heat resistance and acousticproperties.

Example 13

A biaxially oriented polyphenylene sulfide film was obtained in the samemanner as in Example 9 except that as a compatible plasticizer,bisphenol A type epoxy resin (“Epicoat” 1004 manufactured by Yuka-ShellEpoxy Co., Ltd.) of 2 parts by weight was compounded in Example 9. Themeasurement and evaluation results on the constitution andcharacteristic of the biaxially oriented polyphenylene sulfide filmobtained were shown in Table 1. The biaxially oriented polyphenylenesulfide film obtained was deteriorated in molding processability

Example 14

A biaxially oriented polyphenylene sulfide film was obtained in the samemanner as in Example 3 except that as a thermoplastic resin (Y),polyether sulfone (“RADEL” manufactured by Amoco Corporation) (PES) wasused. The measurement and evaluation results on the constitution andcharacteristic of the biaxially oriented polyphenylene sulfide filmobtained are shown in Table 1, and the biaxially oriented polyphenylenesulfide film obtained in the present Example was excellent in moldingprocessability, heat resistance and acoustic properties.

Example 15

A biaxially oriented polyphenylene sulfide film was obtained in the samemanner as in Example 3 except that as a thermoplastic resin (Y),polysulfone (“UDEL” manufactured by Amoco Corporation) (PSF) was used.The measurement and evaluation results on the constitution andcharacteristic of the biaxially oriented polyphenylene sulfide filmobtained are shown in Table 1, and the biaxially oriented polyphenylenesulfide film obtained in the present Example was excellent in moldingprocessability, heat resistance and acoustic properties.

Example 16

PPS resin produced in Reference example 1 of 90 parts by weight wasdried at 180° C. under reduced pressure for 3 hours, as a thermoplasticresin (Y), nylon 610 resin (nylon resin, “Amilan CM2001” manufactured byToray Industries Inc., polyamide-1 (PA-1)) of 10 parts by weight wasdried at 120° C. under reduced pressure for 3 hours, further, as acompatible plasticizer, bisphenol A type epoxy resin (“Epicoat” 1004manufactured by Yuka-Shell Epoxy Co., Ltd.) of 2 parts by weight wascompounded to 100 parts by weight in total of the PPS resin and nylon610, then charged in a co-rotational biaxial kneading extruder having avent provided with three kneading paddle mixing parts being heated at330° C. (manufactured by Japan Steel Works Ltd., screw diameter 30 mm,screw length/screw diameter 45.5), and melt extruded in a strand form byresidence time of 90 seconds and screw rotation number of 300 rpm/min,cooled in water at 25° C., then immediately cut to produce a blend chip.A raw material that 0.3 wt % of calcium carbonate powder having anaverage particle diameter of 1.2 μm and 0.05 wt % of calcium stearatewere added to 100 parts by weight of the blend chip of PPS/PA-1 (90/10wt %) and uniformly dispersed/compounded raw material was dried at 150°C. under reduced pressure for 3 hours, and then fed to a uniaxialextruder of full-flight that the melt part was heated at 320° C.

Next, the polymer melted by the extruder was filtered trough a filterwhose temperature was set at 320° C., melt-extruded from a T-die set at320° C., and then closely contacted on a cast drum of surfacetemperature at 25° C. while applying static charge thereon to be cooledand solidified, thereby to produce an unstretched polyphenylene sulfidefilm.

This unstretched polyphenylene sulfide film was stretched at 110° C. by2.8 times in a longitudinal direction of film by using a longitudinalstretch machine constituted by a plurality of rolls heated and byutilizing circumferential velocity difference between rolls. Thereafter,the film edges were removed, thereby to produce a biaxially orientedpolyphenylene sulfide film of 30 μm in thickness.

The measurement and evaluation results on the constitution andcharacteristic of the uniaxially oriented polyphenylene sulfide filmobtained are shown in Table 1, and this uniaxially orientedpolyphenylene sulfide film was excellent in molding processability, wassomewhat inferior in heat resistance and acoustic properties, but was alevel usable in practice.

Example 17

PPS resin produced in Reference example 1 of 90 parts by weight wasdried at 180° C. under reduced pressure for 3 hours, as a thermoplasticresin (Y), nylon 610 resin (nylon resin, “Amilan CM2001” manufactured byToray Industries Inc., polyamide-1 (PA-1)) of 10 parts by weight wasdried at 120° C. under reduced pressure for 3 hours, further, as acompatible plasticizer, bisphenol A type epoxy resin (“Epicoat” 1004manufactured by Yuka-Shell Epoxy Co., Ltd.) of 2 parts by weight wascompounded to 100 parts by weight in total of the PPS resin and nylon610, then charged in a co-rotational biaxial kneading extruder having avent provided with three kneading paddle mixing parts being heated at330° C. (manufactured by Japan Steel Works Ltd., screw diameter 30 mm,screw length/screw diameter 45.5), and melt extruded in a strand form byresidence time of 90 seconds and screw rotation number of 300 rpm/min,cooled in water at 25° C., then immediately cut to produce a blend chip.A raw material that 0.3 wt % of calcium carbonate powder having anaverage particle diameter of 1.2 μm and 0.05 wt % of calcium stearatewere added to 100 parts by weight of the blend chip of PPS/PA-1 (90/10wt %) and uniformly dispersed/compounded raw material was dried at 150°C. under reduced pressure for 3 hours, and then fed to a uniaxialextruder of full-flight that the melt part was heated at 320° C.

Next, the polymer melted by the extruder was filtered trough a filterwhose temperature was set at 320° C., melt-extruded from a T-die set at320° C., and then closely contacted on a cast drum of surfacetemperature at 25° C. while applying static charge thereon to be cooledand solidified, thereby to produce an unstretched polyphenylene sulfidefilm. The measurement and evaluation results on the constitution andcharacteristic of the unoriented polyphenylene sulfide film obtained areshown in Table 1, and this unoriented polyphenylene sulfide film wassomewhat inferior in molding processability, heat resistance andacoustic properties, but was a level usable in practice.

Examples 18, 19

A biaxially oriented polyphenylene sulfide film was obtained in the samemanner as in Example 3 except that film thickness of the biaxiallyoriented polyphenylene sulfide film was changed as shown in Table 1. Themeasurement and evaluation results on the constitution andcharacteristic of the biaxially oriented polyphenylene sulfide filmobtained were shown in Table 1. The biaxially oriented polyphenylenesulfide film obtained in Example 18 was somewhat inferior in moldingprocessability, but was a level usable in practice, and was excellent inheat resistance and acoustic properties. The biaxially orientedpolyphenylene sulfide film obtained in Example 19 was somewhat inferiorin acoustic properties, but was a level usable in practice, and wasexcellent in molding processability and heat resistance.

Comparative Example 1

A biaxially oriented polyphenylene sulfide film was obtained in the samemanner as in Example 1 except that draw ratio in the film formingcondition of biaxially oriented polyphenylene sulfide film was changedas shown in Table 1. The biaxially oriented polyphenylene sulfide filmobtained in the present Comparative example was excellent in heatresistance, somewhat inferior in acoustic properties, but was a levelusable in practice, and insufficient in molding processability becauseit was lacking in elongation at break.

Comparative Example 2

A raw material that 0.3 wt % of calcium carbonate powder having anaverage particle diameter of 1.2 μm and 0.05 wt % of calcium stearatewere added to 100 parts by weight of the PPS resin produced in Referenceexample 1 and uniformly dispersed/compounded raw material was dried at150° C. under reduced pressure for 3 hours, and then fed to a uniaxialextruder of full-flight that the melt part was heated at 320° C. Next,the polymer melted by the extruder was filtered trough a filter whosetemperature was set at 320° C., melt-extruded from a T-die set at 320°C., and then closely contacted on a cast drum of surface temperature at25° C. while applying static charge thereon to be cooled and solidified,thereby to produce an unstretched polyphenylene sulfide film. Theunstretched polyphenylene sulfide film obtained in the presentComparative example was lacking in elongation at break, inferior inmolding processability, and also insufficient in acoustic properties andheat resistance.

Comparative Example 3

A biaxially oriented polyphenylene sulfide film was obtained in the samemanner as in Example 3 except that the added amount of PA-1 as athermoplastic resin (Y) was changed as shown in Table 1. The measurementand evaluation results on the constitution and characteristic of thebiaxially oriented polyphenylene sulfide film obtained were shown inTable 1. The biaxially oriented polyphenylene sulfide film obtained inthe present Comparative example was inferior in molding processabilityand acoustic properties due to low Young' modulus, and also insufficientin heat resistance.

Comparative Example 4

A biaxially oriented polyphenylene sulfide film was obtained in the samemanner as in Example 9 except that the added amount of PEI as athermoplastic resin (Y) was changed as shown in Table 1. The measurementand evaluation results on the constitution and characteristic of thebiaxially oriented polyphenylene sulfide film obtained were shown inTable 1. The biaxially oriented polyphenylene sulfide film obtained wasinsufficient in molding processability and acoustic properties.

Comparative Example 5

PEN chip of 100 parts by weight produced in Reference example 3 wasdried at 180° C. under reduced pressure for 3 hours, and then fed to auniaxial extruder of full-flight that the melt part was heated at 320°C.

Next, the polymer melted by the extruder was filtered trough a filterwhose temperature was set at 320° C., melt-extruded from a T-die set at320° C., and then closely contacted on a cast drum of surfacetemperature at 25° C. while applying static charge thereon to be cooledand solidified, thereby to produce an unstretched PEN film.

This unstretched PEN film was stretched at 140° C. by 4.0 times in alongitudinal direction of film by using a longitudinal stretch machineconstituted by a plurality of rolls heated and by utilizingcircumferential velocity difference between rolls. Thereafter, this filmwas introduced to a tenter while holding both ends by clips, stretchedat a draw temperature of 145° C. by a draw ratio of 4.0 in a widthdirection of film, followed by heat treatment at a temperature of 265°C. for 4 seconds, then subjected to a 5% relaxing treatment in a lateraldirection in a cool zone controlled at 150° C., cooled to roomtemperature, and the film edges were removed, thereby to produce abiaxially oriented PEN film of 30 μm in thickness.

The measurement and evaluation results on the constitution andcharacteristic of the biaxially oriented polyphenylene sulfide filmobtained are shown in Table 1, and this biaxially oriented PEN film wasexcellent in heat resistance and acoustic properties, but lacking inelongation at break, and inferior in molding processability.

TABLE 1 Thermoplastic resin Compatible Polyarylene sulfide (T)plasticizer Film-forming condition Content Content Content Heat-setRelaxing (part by (part by (part by Orientation Draw ratio temperaturetreatment in TD Kind weight %) Kind weight %) Kind weight %) state offilm (MD/TD) (° C.) direction (%) Example 1 PPS 100 None — C1 — Biaxial3.3/3.3 265 5 orientation Example 2 PPS 100 None — C1 — Biaxial 3.7/3.5265 5 orientation Example 3 PPS 90 PA-1 10 C1 0.5 Biaxial 2.8/2.8 265 5orientation Example 4 PPS 70 PA-1 30 C1 1.5 Biaxial 2.8/2.8 265 5orientation Example 5 PPS 85 PA-1 45 C1 2 Biaxial 2.8/2.8 265 5orientation Example 6 PPS 97 PA-1 3 C1 0.3 Biaxial 2.8/2.8 265 5orientation Example 7 PPS 90 PA-2 10 C1 0.5 Biaxial 2.8/2.8 265 5orientation Example 8 PPS 90 PA-3 10 C1 0.5 Biaxial 2.8/2.8 265 5orientation Example 9 PPS 90 PEI 10 C1 0.5 Biaxial 2.8/2.8 265 5orientation Example 10 PPS 90 PEI 5 C1 0.3 Biaxial 2.8/2.8 265 5orientation Example 11 PPS 90 PEI 15 C1 1 Biaxial 2.8/2.8 265 5orientation Example 12 PPS 90 PEI 10 C1 0.5 Biaxial 3.0/3.0 265 5orientation Example 13 PPS 90 PEI 10 C2 0.5 Biaxial 2.8/2.8 265 5orientation Example 14 PPS 90 PES 10 C1 0.5 Biaxial 2.8/2.8 265 5orientation Example 15 PPS 90 PSF 10 C1 0.5 Biaxial 2.8/2.8 265 5orientation Example 16 PPS 90 PA-1 10 C2 2 Uniaxial only MD 3.3 — —orientation Example 17 PPS 90 PA-1 10 C2 2 Monorientation — — — Example18 PPS 90 PA-1 10 C1 0.5 Biaxial 2.8/2.8 265 5 orientation Example 19PPS 90 PA-1 10 C1 0.5 Biaxial 2.8/2.8 265 5 orientation Comparative PPS100 None — — — Biaxial 4.0/4.0 265 5 Example 1 orientation ComparativePPS 100 None — — — Honorientation — — — Example 2 Comparative PPS 40PA-1 60 C1 3 Biaxial 2.8/2.8 265 5 Example 3 orientation Comparative PPS90 PEI 50 C1 2.5 Biaxial 2.8/2.8 265 5 Example 4 orientation ComparativePEN 100 — — — — Biaxial 4.0/4.0 260 4 Example 5 orientation GlassElongation Film transition at break Young's Molding thickness Existanceof temperature MD/TD modulus processability Heat Acoustic (μm) siloxanebond (° C.) (%) MD/TD 1 resistance property Example 1 30 — 93 105/1153.3/3.2 ◯  ◯ Example 2 ″ — 93  90/110 3.6/3.5 ◯  ◯ Example 3 ″ ◯ 93150/165 2.4/2.6    Example 4 ″ ◯ 93 160/170 2.3/2.4    Example 5 ″◯ 93 175/190 1.8/1.8  ◯  Example 6 ″ ◯ 93 110/120 2.6/2.8 ◯  Example 7 ″ ◯ 93 145/160 2.6/2.7    Example 8 ″ ◯ 93 140/155 2.6/2.7   Example 9 ″ ◯ 93 145/155 2.7/2.8    Example 10 ″ ◯ 93  50/1002.6/2.7    Example 11 ″ ◯ 93  80/100 2.9/2.9 ◯ ◯ ◯ Example 12 ″ ◯ 93130/80  2.7/3.0 ◯   Example 13 ″ • 93  70/100 2.6/2.7 Δ ◯ ◯ Example 14″ ◯ 93 135/140 2.7/2.7    Example 15 ″ ◯ 93 135/140 2.6/2.6   Example 16 ″ ″ 91 130/105 2.1/2.7  ◯ ◯ Example 17 ″ ″ 90 105/1051.5/1.5 ◯ ◯ ◯ Example 18 10 ◯ 93 100/110 2.6/2.6 ◯   Example 19 100 ◯93 135/140 2.3/2.3   ◯ Comparative 30 — 93 80/90 3.8/3.8 Δ  ◯ Example1 Comparative ″ — 90 4/4 1.6/1.6 ″ ″ ″ Example 2 Comparative ″ ◯ 93180/190 1.4/1.3 ″ ″ ″ Example 3 Comparative ″ ◯ 93 40/40 2.6/2.8 ″  ″Example 4 Comparative ″ — 120 80/80 6.0/6.0 ″   Example 5 Remarks: MD:longitudinal direction of film, TD: width direction of film PEI:Polyetherimide PES: Polyether sulfide PSF: Polysulfone PEN:Polyethylene-2,6-napthalate C1: Isocyanotasilane (KBI9007) C2: Epicoat(1004)

Example 20

PPS resin produced in Reference example 1 of 80 parts by weight andcalcium carbonate of 20 parts by weight having a particle diameter of1.2 μm as an inert particle were compounded and charged in aco-rotational biaxial kneading extruder having a vent being heated at300° C. (manufactured by Japan Steel Works Ltd., screw diameter 30 mm,screw length/screw diameter=45.5), and melt extruded in a strand form byresidence time of 90 seconds and screw rotation number of 300 rpm/min,cooled in water at 25° C., then immediately cut to produce a 20 wt %particle master chip.

Next, using 50 parts by weight of PPS resin produced in Referenceexample 1 and 10 parts by weight of polyetherimide (“Ultem 1010”manufactured by GE Plastics Corporation) (PEI) as a thermoplastic resin(Y), as a compatible plasticizer, 0.375 wt % ofγ-isocyanatepropyltriethoxysilane (“KBE9007” manufactured by Shin-EtsuChemical co., Ltd.) relative to the whole polymer was compounded, andthese were charged in a co-rotational biaxial kneading extruder having avent being heated at 300° C. (manufactured by Japan Steel Works Ltd.,screw diameter 30 mm, screw length/screw diameter=45.5), and meltextruded in a strand form by residence time of 90 seconds and screwrotation number of 300 rpm/min, cooled in water at 25° C., thenimmediately cut to produce a blend chip. Sixty parts by weight of theblend chip raw material of PPS/PEI (16.7 wt %) and 50 parts by weight ofthe 20 wt % particle master chip previously produced were compounded,dried at 150° C. under reduced pressure for 3 hours, thereafter, 0.05 wt% of calcium stearate was added relative to the whole chip, and fed to auniaxial extruder of full-flight that the melt part was heated at 320°C.

Next, the polymer melted by the extruder was filtered trough a filterwhose temperature was set at 320° C., melt-extruded from a T-die set at320° C., and then closely contacted on a cast drum of surfacetemperature at 25° C. while applying static charge thereon to be cooledand solidified, thereby to produce an unstretched polyphenylene sulfidefilm.

This unstretched polyphenylene sulfide film was stretched at 110° C. by2.8 times in a longitudinal direction of film by using a longitudinalstretch machine constituted by a plurality of rolls heated and byutilizing circumferential velocity difference between rolls. Thereafter,this film was introduced to a tenter while holding both ends by clips,stretched at a draw temperature of 110° C. by a draw ratio of 3.0 in awidth direction of film, followed by heat treatment at a temperature of265° C. for 5 seconds, then subjected to a 3% relaxing treatment in alateral direction in a cool zone controlled at 150° C., cooled to roomtemperature, and the film edges were removed, thereby to produce abiaxially oriented polyphenylene sulfide film of 30 μm in thicknesscontaining 10 parts by weight of calcium carbonate particle relative to100 parts by weight of the whole polymer.

The measurement and evaluation results on the constitution andcharacteristic of the biaxially oriented polyphenylene sulfide filmobtained are shown in Table 2, and this biaxially oriented polyphenylenesulfide film was excellent in heat molding processability.

Examples 21, 22, 23

A biaxially oriented polyphenylene sulfide film was obtained in the samemanner as in Example 20 except that the added amount of polyetherimideas a thermoplastic resin (Y) relative to the whole polymer was changedas shown in Table 2. The measurement and evaluation results on theconstitution and characteristic of the biaxially oriented polyphenylenesulfide film obtained were shown in Table 2. The biaxially orientedpolyphenylene sulfide film obtained in Example 21 was excellent in heatmolding processability. Regarding the biaxially oriented polyphenylenesulfide film obtained in Example 22, when it was heat molded at 180° C.,breakage of film occurred, but when it was heat molded at 230° C., nobreakage of film occurred and it was able to be formed. Taking-out aftermolding and shape retention property were good both at 100° C. and 120°C. Regarding the biaxially oriented polyphenylene sulfide film obtainedin Example 23, when it was heat molded at 180° C., breakage of filmoccurred, but when it was heat molded at 230° C., no breakage of filmoccurred and it was able to be molded. Taking-out after molding andshape retention property were good both at 100° C. and 120° C.

Example 24

A biaxially oriented polyphenylene sulfide film was obtained in the samemanner as in Example 20 except that calcium carbonate having a particlediameter of 0.6 μm was used as an inert particle. The measurement andevaluation results on the constitution and characteristic of thebiaxially oriented polyphenylene sulfide film obtained are shown inTable 2, and the film was excellent in heat moldability.

Example 25

A biaxially oriented polyphenylene sulfide film was obtained in the samemanner as in Example 20 except that the content of calcium carbonate asan inert particle was set to 3 parts by weight relative to 100 parts byweight of the whole polymer. The measurement and evaluation results onthe constitution and characteristic of the biaxially orientedpolyphenylene sulfide film obtained are shown in Table 2, and the filmwas excellent in heat moldability.

Example 26

A biaxially oriented polyphenylene sulfide film was obtained in the samemanner as in Example 20 except that silica of 0.6 μm was used as aninert particle. The measurement and evaluation results on theconstitution and characteristic of the biaxially oriented polyphenylenesulfide film obtained are shown in Table 2, and the film was excellentin heat molding.

Example 27

A biaxially oriented polyphenylene sulfide film was obtained in the samemanner as in Example 1 except that as a thermoplastic resin (Y), nylon610 resin (nylon resin, “Amilan CM2001” manufactured by Toray IndustriesInc) was used. The measurement and evaluation results on theconstitution and characteristic of the biaxially oriented polyphenylenesulfide film obtained are shown in Table 2, and when the film was heatmolded at 180° C., breakage of film occurred, but when it was heatmolded at 230° C., no breakage of film occurred and it was able to bemolded. Taking-out after molding and shape retention property were goodboth at 100° C. and 120° C.

Example 28

A biaxially oriented polyphenylene sulfide film was obtained in the samemanner as in Example 20 except that the content of calcium carbonatepowder having an average particle diameter of 1.2 μm was set to 3 partsby weight. The measurement and evaluation results on the constitutionand characteristic of the biaxially oriented polyphenylene sulfide filmobtained are shown in Table 2, and when the film was heat molded both at180° C. and 230° C., no breakage of film occurred, but the demoldingproperty after heat molding at 120° C. was bad.

Comparative Example 6

A biaxially oriented polyphenylene sulfide film was obtained in the samemanner as in Example 20 except that as a thermoplastic resin (Y),polysulfone (“UDEL” manufactured by Amoco Corporation) (PSF) was used.The measurement and evaluation results on the constitution andcharacteristic of the biaxially oriented polyphenylene sulfide filmobtained are shown in Table 2, and when the film was heat molded at 180°C., breakage of film occurred, but when it was heat molded at 230° C.,no breakage of film occurred and it was able to be molded. Further,taking-out property after molding and shape retention property were good

Comparative Example 7

A biaxially oriented polyphenylene sulfide film was obtained in the samemanner as in Example 20 except that draw ratio in the film-formingcondition of biaxially oriented polyphenylene sulfide film was set to3.9×3.4. The measurement and evaluation results on the constitution andcharacteristic of the biaxially oriented polyphenylene sulfide filmobtained are shown in Table 2, and when the film was heat molded at 180°C., breakage of film occurred, but when it was heat molded at 230° C.,no breakage of film occurred and it was able to be molded. Taking-outafter molding and shape retention property were good both at 100° C. and120° C.

Comparative Example 8

An unoriented polyphenylene sulfide film was produced in the same manneras in Example 20 except that 0.3 parts by weight of calcium carbonatepowder having an average particle diameter of 1.2 μm was added to 100parts by weight of the PPS resin produced in Reference example 1. Next,a biaxially oriented polyphenylene sulfide film was obtained in the samemanner as in Example 1 except that draw ratio in the film-formingcondition was set to 3.9×3.4. The measurement and evaluation results onthe constitution and characteristic of the biaxially orientedpolyphenylene sulfide film obtained are shown in Table 2, and because oflow elongation at break, breakage of film occurred when the film washeat molded both at 180° C. and 230° C.

Comparative Example 9

A biaxially oriented polyphenylene sulfide film was obtained in the samemanner as in Example 20 except that 10 parts by weight of calciumcarbonate powder having an average particle diameter of 1.2 μm was usedto 90 parts by weight of the PPS resin produced in Reference example 1.The measurement and evaluation results on the constitution andcharacteristic of the biaxially oriented polyphenylene sulfide filmobtained are shown in Table 2, and because of low elongation at break,breakage of film occurred when the film was heat molded both at 180° C.and 230° C.

TABLE 2 Polyarylene sulfide Thermoplastic resin (T) Compatible Inertparticle Film- Content to Content to Average plasticizer Content to 100forming whole polymer whole polymer dispersion Content parts by weightof Particle condition (part by (part by diameter (part by whole polymerdiameter Draw ratio Kind weight %) Kind weight %) (μm) Kind weight %)Kind (part by weight) (μm) MD/TD Example 20 PPS 90 PEI 10 0.15 C1 0.375Calcium 10 1.2 2.8-3.2 carbonate Example 21 PPS 85 PEI 15 0.35 C1 1.0Calcium 10 1.2 2.8-3.2 carbonate Example 22 PPS 96 PEI 5 0.15 C1 0.375Calcium 10 1.2 2.8-3.2 carbonate Example 23 PPS 97 PEI 3 0.15 C1 0.375Calcium 10 1.2 2.8-3.2 carbonate Example 24 PPS 90 PEI 10 0.25 C1 0.375Calcium 10 0.6 2.8-3.2 carbonate Example 25 PPS 98 PEI 10 0.25 C1 0.375Calcium 3 1.2 2.8-3.2 carbonate Example 26 PPS 90 PEI 10 0.25 C1 0.375Silica 10 0.6 2.8-3.2 Example 27 PPS 98 N410 10 0.25 C1 0.375 Calcium 101.2 2.8-3.2 carbonate Example 28 PPS 90 PEI 10 0.25 C1 0.375 Calcium 0.31.2 2.8-3.2 carbonate Comparative PPS 98 PSF 10 0.75 C1 0.375 Calcium 101.2 2.8-3.2 Example 6 carbonate Comparative PPS 90 PEI 10 0.40 C1 0.375Calcium 10 1.2 3.9-3.4 Example 7 carbonate Comparative PPS 100 — — — C10.375 — — — 3.9-3.4 Example 8 Comparative PPS 90 — — — C1 0.375 Calcium10 1.2 2.8-3.2 Example 9 carbonate Room temperature MechanicalTaking-out Glass Resistance Elongation property(120° C.) property aftertransition of at break Elongation Young's Heat molding and shapetemperature siloxane MD/TD at break modulus moldability retentionproperty (° C.) bond (%) (%) (CDA) 100° C. 230° C. 100° C. 120° C.Example 20 93 ◯ 105/75 200 1.2 ◯ ◯ ◯ ◯ Example 21 93 ◯ 108/70 195 1.3 ◯◯ ◯ ◯ Example 22 93 ◯ 120/90 160 0.8 ″ ◯ ◯ ◯ Example 23 93 ◯ 100/70 1100.6 ″ ◯ ◯ ◯ Example 24 93 ◯ 100/70 191 1.0 ◯ ◯ ◯ ◯ Example 25 93 ◯110/80 191 8.8 ◯ ◯ ◯ ◯ Example 26 93 ◯ 101/71 190 1.0 ◯ ◯ ◯ ◯ Example 2793 ◯ 110/80 200 0.3 ″ ◯ ◯ ◯ Example 28 93 ◯ 130/30 190 8.8 ◯ ◯ ◯ ″Comparative 93 ◯  60/80 180 1.0 ″ ◯ ◯ ◯ Example 6 Comparative 93 ◯ 60/80 140 1.3 ″ ◯ ◯ ◯ Example 7 Comparative 93 —  60/80 120 1.2 ″ ″ — —Example 8 Comparative 93 —  50/40 100 0.9 ″ ″ — — Example 9 Remarks:PEI: Polyetherimide N410: Nylon 410 PSF: Polysulfone C1:Isocyanotasilane (KBI9007) C2: Epicoat (1004)

INDUSTRIAL APPLICABILITY

The polyarylene sulfide film of the present invention can be preferablyused as a film for an acoustic instrument vibrating plate constitutingvarious acoustic instruments, that is, speakers.

1. A polyarylene sulfide film wherein the elongation at break in eithera longitudinal direction or a width direction of the film is 100% ormore and 250% or less, and the Young's modulus in either a longitudinaldirection or a width direction of the film is 1.5 GPa or more and lessthan 4 GPa.
 2. The polyarylene sulfide film of claim 1, wherein theelongation at break in both a longitudinal direction and a widthdirection of the film is 100% or more and 250% or less, and the Young'smodulus in both a longitudinal direction and a width direction of thefilm is 1.5 GPa or more and less than 4 GPa.
 3. The polyarylene sulfidefilm of claim 1, wherein the thickness of the film is 3 μm or more and100 μm or less.
 4. The polyarylene sulfide film of claim 1, comprising athermoplastic resin (Y) other than polyarylene sulfide, wherein thecontent of the thermoplastic resin (Y) is 1 to 40 parts by weight whenthe sum of contents of polyarylene sulfide and the thermoplastic resin(Y) is 100 parts by weight.
 5. The polyarylene sulfide film of claim 1,comprising an inert particle by 0.1 to 30 parts by weight relative to100 parts by weight in total of polymers constituting the film.
 6. Thepolyarylene sulfide film of claim 4, comprising an inert particle by 0.6to 30 parts by weight relative to 100 parts by weight in total ofpolymers constituting the film, and a thermoplastic resin (Y) other thanpolyarylene sulfide by 1 to 40 parts by weight relative to 100 parts byweight in total of polymers constituting the film.
 7. The polyarylenesulfide film of claim 5, wherein the particle diameter of the inertparticle is 0.1 μm or more and 3 μm or less.
 8. The polyarylene sulfidefilm of claim 5, wherein the inert particle is at least one kindselected from calcium carbonate and silica.
 9. The polyarylene sulfidefilm of claim 4, wherein the thermoplastic resin (Y) is at least onekind selected from the group consisting of polyamide, polyetherimide,polysulfone and polyether sulfone.
 10. The polyarylene sulfide film ofclaim 4, wherein the average dispersion diameter of the thermoplasticresin (Y) is 0.01 to 2 μm.
 11. The polyarylene sulfide film of claim 4,wherein the average dispersion diameter of the thermoplastic resin (Y)is 0.05 to 0.5 μm.
 12. The polyarylene sulfide film of claim 1, whereinthe polyarylene sulfide is polyphenylene sulfide.
 13. The polyarylenesulfide film of claim 1, which is a film for heat molding.
 14. Thepolyarylene sulfide film of claim 1, which is a film for an acousticinstrument vibrating plate.
 15. The polyarylene sulfide film of claim 1,wherein the glass transition temperature thereof is observed at 85° C.or more to less than 95° C., and not observed at 95° C. or more to 130°C. or less.
 16. The polyarylene sulfide film of claim 4, comprising asilicon atom constituting a siloxane bond in an interface of a dispersedphase composed of the thermoplastic resin (Y).
 17. A method of producingthe polyarylene sulfide film of claim 1, comprising the step ofsubjecting a resin composition obtained by kneading raw materialscomprising polyarylene sulfide, thermoplastic resin (Y), and 0.1 to 10parts by weight of a compatible plasticizer having at least one kind ofgroup selected from the group consisting of an epoxy group, an aminogroup and an isocyanate group to a melt film-forming.